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Sample records for lanthanideiii coordination polymers

  1. Increasing the luminescence of lanthanide(III) macrocyclic complexes by the use of polymers and lanthanide enhanced luminescence

    NASA Astrophysics Data System (ADS)

    Leif, Robert C.; Becker, Margie C.; Bromm, Alfred J., Jr.; Vallarino, Lidia M.; Williams, Steven A.; Yang, Sean

    2001-05-01

    A Eu (III)-macrocycle-isothiocyanate, Quantum DyeTM, has been reacted with lysine homo- and hetero-peptides to give polymers with multiple luminescent side chains. Contrary to the concentration quenching that occurs with conventional organic fluorophores, the attachment of multiple Quantum Dyes to a polymer results in a concomitant increase in luminescence. The emission intensity of the peptide-bound Quantum Dye units is approximately linearly related to their number. The attachment of peptides containing multiple lanthanide (III) macrocycles to analyte-binding species is facilitated by employing solid-phase technology. Bead-bound peptides are first labeled with multiple Quantum Dye units, then conjugated to an antibody, and finally released from the bead by specific cleavage with Proteinase K unedr physiological conditions. Since the luminescence of lanthanide(III) macrocycles is enhanced by the presence of GD(III) or Y(III) ions in a micellar system, a significant increase in signal can be achieved by attaching a polymer labeled with multiple Quantum Dye units to an analyte- binding species, such as a monoclonal antibody, or by taking advantage of the luminescence enhancing effects of Gd(III) or Y(III), or by both approaches concomitantly. A comparison between the integrated intensity and lifetime measurements of the Eu(III)-macrocycle under a variety of conditions show that the signal increase caused by Gd(III) can not be explained solely by the increase in lifetime, and must result in significant part from an energy transfer process invloving donors not directly bound to the Eu(III).

  2. Selective Retention of Explosives and Related Compounds on Gas-Chromatographic Capillary Columns Coated with Lanthanide(III) ß-diketonate Polymers

    SciTech Connect

    Harvey, Scott D.; Wenzel, Thomas J.

    2009-09-04

    The purpose of this research was to investigate coating capillary columns with lanthanide(III) beta-diketonate polymers to provide gas-chromatographic columns with selectivity toward explosives and related compounds. Capillary columns were statically coated with a combination of a lanthanide(III) beta-diketonate polymer, which utilized p-di(4,4,5,5,6,6,6-heptafluoro-1,3-hexanedionyl)benzene (dihed) as a ligand, and SE-30. A novel coating technique was developed that used a methanol-containing azeotrope to provide solubility for both polymers while maintaining a low boiling point compatible with static coating. As based on temperature-programmed retention indices, the custom experimental columns displayed selective retention of nitroaromatic, nitroalkane, and nitrate ester test probes relative to an appropriate SE-30 control column. Selective retention was more pronounced for strong Lewis base analytes (i.e., cyclohexanone). Relative analyte retention on the La(dihed), Tb(dihed) and Eu(dihed) columns are discussed relative to Lewis acidity and solubility of the polymer in the azeotrope coating solution.

  3. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

    Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

    2012-12-04

    A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

  4. Porphyrin coordination polymer nanospheres and nanorods

    DOEpatents

    Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

    2013-09-10

    A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

  5. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    SciTech Connect

    Nune, Satish K.; Thallapally, Praveen K.; McGrail, Benard Peter; Annapureddy, Harsha V. R.; Dang, Liem X.; Mei, Donghai; Karri, Naveen; Alvine, Kyle J.; Olszta, Matthew J.; Arey, Bruce W.; Dohnalkova, Alice

    2015-10-07

    Nanoscale porous coordination polymers were synthesized using simple wet chemical method. The effect of various polymer surfactants on colloidal stability and shape selectivity was investigated. Our results suggest that the nanoparticles exhibited significantly improved adsorption kinetics compared to bulk crystals due to decreased diffusion path lengths and preferred crystal plane interaction.

  6. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with α-hydroxyisobutyric acid.

    PubMed

    Chen, Xiao-Yan; Goff, George S; Ewing, William C; Scott, Brian L; Runde, Wolfgang

    2012-12-17

    Despite the wide range of applications of α-hydroxyisobutyric acid (HIBA) in biochemical processes, pharmaceutical formulations, and group and elemental separations of lanthanides and actinides, the structures and geometries of lanthanide-HIBA complexes are still not well understood. We reacted HIBA with lanthanides in aqueous solution at pH = 5 and synthesized 14 lanthanide-HIBA complexes of the formula [Ln(HIBA)(2)(H(2)O)(2)](NO(3))·H(2)O (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14)), isolating single crystals (1-7, 10, and 11) and powders (8, 9, and 12-14). Both single-crystal and powder X-ray diffraction studies reveal a two-dimensional extended structure across the entire lanthanide series. The environment around the eight-coordinated Ln(III) atom is best described as a distorted dodecahedron, where HIBA acts as a monoanionic tridentate ligand with one carboxylato oxygen atom and one hydroxyl oxygen atom chelating to one Ln(III) center. The carboxylato oxygen atom from a second HIBA ligand bridges to a neighboring Ln(III) atom to form a two-dimensional extended structure. While the coordination mode for HIBA is identical across the lanthanide series, three different structure types are found for La, Ce-Ho, and Er-Lu. Solution characterization using (13)C NMR further confirmed a single solution complex under the crystallization conditions. Raman and UV-vis-NIR absorbance and diffuse reflectance spectra of HIBA-Ln(III) complexes were also measured.

  7. A series of Zn-4f heterometallic coordination polymers and a zinc complex containing a flexible mixed donor dicarboxylate ligand.

    PubMed

    Feng, Xun; Feng, Yu-Quan; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Ng, Seik-Weng

    2013-06-01

    A new zinc compound, together with a corresponding series of Zn-4f heterometallic coordination polymers, namely, [Zn(H2PBDA)(PBDA)]n (1), {[Ln2(PBDA)2·2H2O] [Zn2(PBDA)2Cl2]}n [H2PBDA = 3-(pyridin-3-yl-oxy) benzene-1,2-dicarboxylic acid, and Ln = Pr(2), Nd(3), Eu(4), Gd(5), Dy(6), Ho(7), Er(8)] have been hydrothermally synthesized and characterized systematically. Polymers 2-8 feature two-dimensional (2D) 4,4 networks, containing the original 1D heterometallic double stranded chains composed of [Ln2Zn2(PBDA)2] entities. The extensive hydrogen bonding and π-π stacking interactions were observed to stabilize the extended architectures. The luminescence emission spectra of the polymers vary depending on the lanthanide(III) ion present. Informative magnetic susceptibility measurements show that the same carboxylate bridging fashion of the PBDA ligand results in the different magnetic properties occurring within the heterometallic coordination polymers. In addition, polymer 6 exhibits an interesting slow magnetic relaxation behavior at lower temperatures.

  8. Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

    SciTech Connect

    Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E.; Chan, Benny C.; Lill, Daniel T. de

    2015-05-15

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C{sub 6}H{sub 2}O{sub 5})(C{sub 6}H{sub 3}O{sub 5})(H{sub 2}O)]{sub n} (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented. - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted.

  9. Nanometrization of Lanthanide-Based Coordination Polymers.

    PubMed

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers. PMID:26471940

  10. Nanometrization of Lanthanide-Based Coordination Polymers.

    PubMed

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers.

  11. Inorganic nanoparticles in porous coordination polymers.

    PubMed

    Kim, Cho Rong; Uemura, Takashi; Kitagawa, Susumu

    2016-07-21

    Porous coordination polymers (PCPs) have been recently highlighted because of their high synthetic designability in structure and functions. Because of their ordered nanoporous structures with a large surface area and tunable pore surface functionality, PCPs have emerged as a significant class of nanoporous materials with potential applications in gas storage, separation, catalysis, and chemical sensing. Recent research has shown the utility of PCPs as host materials for the confinement of nanoparticles of inorganic polymers (IPs), such as metals, metal oxides, and metal chalcogenides. The fabrication of IP nanoparticles in PCPs (PCP⊃IP) has been studied for manifesting specific nanosized-dependent properties and host-guest synergistic functions. In this review, we describe the recent progress in the accommodation of IPs in the nanochannels of PCPs and the remarkable functions of the composite materials. PMID:27051891

  12. Controlled isotropic or anisotropic nanoscale growth of coordination polymers: formation of hybrid coordination polymer particles.

    PubMed

    Lee, Hee Jung; Cho, Yea Jin; Cho, Won; Oh, Moonhyun

    2013-01-22

    The ability to fabricate multicompositional hybrid materials in a precise and controlled manner is one of the primary goals of modern materials science research. In addition, an understanding of the phenomena associated with the systematic growth of one material on another can facilitate the evolution of multifunctional hybrid materials. Here, we demonstrate precise manipulation of the isotropic and/or anisotropic nanoscale growth of various coordination polymers (CPs) to obtain heterocompositional hybrid coordination polymer particles. Chemical composition analyses conducted at every growth step reveal the formation of accurately assembled hybrid nanoscale CPs, and microscopy images are used to examine the morphology of the particles and visualize the hybrid structures. The dissimilar growth behavior, that is, growth in an isotropic or anisotropic fashion, is found to be dependent on the size of the metal ions involved within the CPs.

  13. pH-Responsive Relaxometric Behaviour of Coordination Polymer Nanoparticles Made of a Stable Macrocyclic Gadolinium Chelate.

    PubMed

    Aríñez-Soriano, Javier; Albalad, Jorge; Carné-Sánchez, Arnau; Bonnet, Célia S; Busqué, Félix; Lorenzo, Julia; Juanhuix, Jordi; Terban, Maxwell W; Imaz, Inhar; Tóth, Éva; Maspoch, Daniel

    2016-09-01

    Lanthanide-containing nanoscale particles have been widely explored for various biomedical purposes, however, they are often prone to metal leaching. Here we have created a new coordination polymer (CP) by applying, for the first time, a stable Gd(III) chelate as building block in order to prevent any fortuitous release of free lanthanide(III) ion. The use of the Gd-DOTA-4AmP complex as a design element in the CP allows not only for enhanced relaxometric properties (maximum r1 =16.4 mm(-1)  s(-1) at 10 MHz), but also for a pH responsiveness (Δr1 =108 % between pH 4 and 6.5), beyond the values obtained for the low molecular weight Gd-DOTA-4AmP itself. The CP can be miniaturised to the nanoscale to form colloids that are stable in physiological saline solution and in cell culture media and does not show cytotoxicity.

  14. pH-Responsive Relaxometric Behaviour of Coordination Polymer Nanoparticles Made of a Stable Macrocyclic Gadolinium Chelate.

    PubMed

    Aríñez-Soriano, Javier; Albalad, Jorge; Carné-Sánchez, Arnau; Bonnet, Célia S; Busqué, Félix; Lorenzo, Julia; Juanhuix, Jordi; Terban, Maxwell W; Imaz, Inhar; Tóth, Éva; Maspoch, Daniel

    2016-09-01

    Lanthanide-containing nanoscale particles have been widely explored for various biomedical purposes, however, they are often prone to metal leaching. Here we have created a new coordination polymer (CP) by applying, for the first time, a stable Gd(III) chelate as building block in order to prevent any fortuitous release of free lanthanide(III) ion. The use of the Gd-DOTA-4AmP complex as a design element in the CP allows not only for enhanced relaxometric properties (maximum r1 =16.4 mm(-1)  s(-1) at 10 MHz), but also for a pH responsiveness (Δr1 =108 % between pH 4 and 6.5), beyond the values obtained for the low molecular weight Gd-DOTA-4AmP itself. The CP can be miniaturised to the nanoscale to form colloids that are stable in physiological saline solution and in cell culture media and does not show cytotoxicity. PMID:27490646

  15. Antibacterial activity of silver camphorimine coordination polymers.

    PubMed

    Cardoso, João M S; Galvão, Adelino M; Guerreiro, Soraia I; Leitão, Jorge H; Suarez, Ana C; Carvalho, M Fernanda N N

    2016-04-28

    Five new silver camphorimine complexes of general formula [Ag(NO3)(Y)L] were synthesized and fully characterized using spectroscopic and analytical techniques. The structure of [Ag(NO3)(OC10H14NC6H4NC10H14O)] () was analyzed using single crystal X-ray diffraction, showing that it arranges as a coordination polymer formed by sequential Ag(NO3) units bridged by the bi-camphor ligand (). The antimicrobial properties of the new complexes were screened using the disk diffusion method and their Minimal Inhibitory Concentrations (MIC) were assessed against selected bacterial strains of the Gram-positive Staphylococcus aureus and the Gram-negative Escherichia coli, Pseudomonas aeruginosa, and Burkholderia contaminans. The lowest MICs were observed for , with estimated values of 72, 20, 32 and 19 μg mL(-1) for S. aureus, E. coli, B. contaminans, and P. aeruginosa, respectively. In the case of S. aureus, similar MIC values were obtained for silver nitrate and compound . All five compounds were bactericidal when used in concentrations equal or above the MIC value, as found by enumerating the total colony forming units (CFUs) after incubation in their presence. PMID:27007331

  16. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with (pyrazol-1-yl)acetic acid.

    PubMed

    Chen, Xiao-Yan; Goff, George S; Scott, Brian L; Janicke, Michael T; Runde, Wolfgang

    2013-03-18

    As a precursor of carboxyl-functionalized task-specific ionic liquids (TSILs) for f-element separations, (pyrazol-1-yl)acetic acid (L) can be deprotonated as a functionalized pyrazolate anion to coordinate with hard metal cations. However, the coordination chemistry of L with f-elements remains unexplored. We reacted L with lanthanides in aqueous solution at pH = 5 and synthesized four lanthanide complexes of general formula [Ln(L)3(H2O)2]·nH2O (1, Ln = La, n = 2; 2, Ln = Ce, n = 2; 3, Ln = Pr, n = 2; 4, Ln = Nd, n = 1). All complexes were characterized by single crystal X-ray diffraction analysis revealing one-dimensional chain formations. Two distinct crystallographic structures are governed by the different coordination modes of carboxylate groups in L: terminal bidentate and bridging tridentate (1-3); terminal bidentate, bridging bidentate, and tridentate coordination in 4. Comparison of the solid state UV-vis-NIR diffuse reflectance spectra with solution state UV-vis-NIR spectra suggests a different species in solution and solid state. The different coordination in solid state and solution was verified by distinctive (13)C NMR signals of the carboxylate groups in the solid state NMR.

  17. Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(III) nitrates: structural, spectroscopic and DFT characterization of the complexes.

    PubMed

    Matveeva, Anna G; Vologzhanina, Anna V; Goryunov, Evgenii I; Aysin, Rinat R; Pasechnik, Margarita P; Matveev, Sergey V; Godovikov, Ivan A; Safiulina, Alfiya M; Brel, Valery K

    2016-03-28

    Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2.

  18. Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

    SciTech Connect

    Cui, Zhongping; Qi, Ji; Xu, Xinxin Liu, Lu; Wang, Yi

    2013-09-15

    To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer composite material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.

  19. Nanoscale coordination polymers for anticancer drug delivery

    NASA Astrophysics Data System (ADS)

    Phillips, Rachel Huxford

    This dissertation reports the synthesis and characterization of nanoscale coordination polymers (NCPs) for anticancer drug delivery. Nanoparticles have been explored in order to address the limitations of small molecule chemotherapeutics. NCPs have been investigated as drug delivery vehicles as they can exhibit the same beneficial properties as the bulk metal-organic frameworks as well as interesting characteristics that are unique to nanomaterials. Gd-MTX (MTX = methotrexate) NCPs with a MTX loading of 71.6 wt% were synthesized and stabilized by encapsulation within a lipid bilayer containing anisamide (AA), a small molecule that targets sigma receptors which are overexpressed in many cancer tissues. Functionalization with AA allows for targeted delivery and controlled release to cancer cells, as shown by enhanced efficacy against leukemia cells. The NCPs were doped with Ru(bpy)32+ (bpy = 2,2'-bipyridine), and this formulation was utilized as an optical imaging agent by confocal microscopy. NCPs containing the chemotherapeutic pemetrexed (PMX) were synthesized using different binding metals. Zr-based materials could not be stabilized by encapsulation with a lipid bilayer, and Gd-based materials showed that PMX had degraded during synthesis. However, Hf-based NCPs containing 19.7 wt% PMX were stabilized by a lipid coating and showed in vitro efficacy against non-small cell lung cancer (NSCLC) cell lines. Enhanced efficacy was observed for formulations containing AA. Additionally, NCP formulations containing the cisplatin prodrug disuccinatocisplatin were prepared; one of these formulations could be stabilized by encapsulation within a lipid layer. Coating with a lipid layer doped with AA rendered this formulation an active targeting agent. The resulting formulation proved more potent than free cisplatin in NSCLC cell lines. Improved NCP uptake was demonstrated by confocal microscopy and competitive binding assays. Finally, a Pt(IV) oxaliplatin prodrug was

  20. Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides.

    PubMed

    Lamprou, Alexandros; Wang, Hongxia; Saeed, Adeela; Svec, Frantisek; Britt, David; Maya, Fernando

    2015-07-14

    We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process. The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications.

  1. Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides.

    PubMed

    Lamprou, Alexandros; Wang, Hongxia; Saeed, Adeela; Svec, Frantisek; Britt, David; Maya, Fernando

    2015-01-01

    We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous polymer monoliths. The developed approach is based on the preparation of a macroporous polymer containing carboxylic acid functional groups and the subsequent step-by-step solution-based controlled growth of a layer of a porous coordination polymer on the surface of the pores of the polymer monolith. The prepared metal-organic polymer hybrid has a high specific micropore surface area. The amount of iron(III) sites is enhanced through metal-organic coordination on the surface of the pores of the functional polymer support. The increase of metal sites is related to the number of iterations of the coating process. The developed preparation scheme is easily adapted to a capillary column format. The functional porous polymer is prepared as a self-contained single-block porous monolith within the capillary, yielding a flow-through separation device with excellent flow permeability and modest back-pressure. The metal-organic polymer hybrid column showed excellent performance for the enrichment of phosphopeptides from digested proteins and their subsequent detection using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The presented experimental protocol is highly versatile, and can be easily implemented to different organic polymer supports and coatings with a plethora of porous coordination polymers and metal-organic frameworks for multiple purification and/or separation applications. PMID:26273850

  2. Central metal ion exchange in a coordination polymer based on lanthanide ions and di(2-ethylhexyl)phosphoric acid: exchange rate and tunable affinity.

    PubMed

    Tasaki-Handa, Yuiko; Abe, Yukie; Ooi, Kenta; Tanaka, Mikiya; Wakisaka, Akihiro

    2014-01-01

    In this paper the exchange of lanthanide(III) ions (Ln(3+)) between a solution and a coordination polymer (CP) of di(2-ethylhexyl)phosphoric acid (Hdehp), [Ln(dehp)3], is studied. Kinetic and selectivity studies suggest that a polymeric network of [Ln(dehp)3] has different characteristics than the corresponding monomeric complex. The reaction rate is remarkably slow and requires over 600 h to reach in nearly equilibrium, and this can be explained by the polymeric crystalline structure and high valency of Ln(3+). The affinity of the exchange reaction reaches a maximum with the Ln(3+) possessing an ionic radius 7% smaller than that of the central Ln(3+), therefore, the affinity of the [Ln(dehp)3] is tunable based on the choice of the central metal ion. Such unique affinity, which differs from the monomeric complex, can be explained by two factors: the coordination preference and steric strain caused by the polymeric structure. The latter likely becomes predominant for Ln(3+) exchange when the ionic radius of the ion in solution is smaller than the original Ln(3+) by more than 7%. Structural studies suggest that the incoming Ln(3+) forms a new phase though an exchange reaction, and this could plausibly cause the structural strain.

  3. Mixing of immiscible polymers using nanoporous coordination templates

    PubMed Central

    Uemura, Takashi; Kaseda, Tetsuya; Sasaki, Yotaro; Inukai, Munehiro; Toriyama, Takaaki; Takahara, Atsushi; Jinnai, Hiroshi; Kitagawa, Susumu

    2015-01-01

    The establishment of methodologies for the mixing of immiscible substances is highly desirable to facilitate the development of fundamental science and materials technology. Herein we describe a new protocol for the compatibilization of immiscible polymers at the molecular level using porous coordination polymers (PCPs) as removable templates. In this process, the typical immiscible polymer pair of polystyrene (PSt) and poly(methyl methacrylate) (PMMA) was prepared via the successive homopolymerizations of their monomers in a PCP to distribute the polymers inside the PCP particles. Subsequent dissolution of the PCP frameworks in a chelator solution affords a PSt/PMMA blend that is homogeneous in the range of several nanometers. Due to the unusual compatibilization, the thermal properties of the polymer blend are remarkably improved compared with the conventional solvent-cast blend. This method is also applicable to the compatibilization of PSt and polyacrylonitrile, which have very different solubility parameters. PMID:26130294

  4. Mixing of immiscible polymers using nanoporous coordination templates.

    PubMed

    Uemura, Takashi; Kaseda, Tetsuya; Sasaki, Yotaro; Inukai, Munehiro; Toriyama, Takaaki; Takahara, Atsushi; Jinnai, Hiroshi; Kitagawa, Susumu

    2015-01-01

    The establishment of methodologies for the mixing of immiscible substances is highly desirable to facilitate the development of fundamental science and materials technology. Herein we describe a new protocol for the compatibilization of immiscible polymers at the molecular level using porous coordination polymers (PCPs) as removable templates. In this process, the typical immiscible polymer pair of polystyrene (PSt) and poly(methyl methacrylate) (PMMA) was prepared via the successive homopolymerizations of their monomers in a PCP to distribute the polymers inside the PCP particles. Subsequent dissolution of the PCP frameworks in a chelator solution affords a PSt/PMMA blend that is homogeneous in the range of several nanometers. Due to the unusual compatibilization, the thermal properties of the polymer blend are remarkably improved compared with the conventional solvent-cast blend. This method is also applicable to the compatibilization of PSt and polyacrylonitrile, which have very different solubility parameters. PMID:26130294

  5. Mixing of immiscible polymers using nanoporous coordination templates

    NASA Astrophysics Data System (ADS)

    Uemura, Takashi; Kaseda, Tetsuya; Sasaki, Yotaro; Inukai, Munehiro; Toriyama, Takaaki; Takahara, Atsushi; Jinnai, Hiroshi; Kitagawa, Susumu

    2015-07-01

    The establishment of methodologies for the mixing of immiscible substances is highly desirable to facilitate the development of fundamental science and materials technology. Herein we describe a new protocol for the compatibilization of immiscible polymers at the molecular level using porous coordination polymers (PCPs) as removable templates. In this process, the typical immiscible polymer pair of polystyrene (PSt) and poly(methyl methacrylate) (PMMA) was prepared via the successive homopolymerizations of their monomers in a PCP to distribute the polymers inside the PCP particles. Subsequent dissolution of the PCP frameworks in a chelator solution affords a PSt/PMMA blend that is homogeneous in the range of several nanometers. Due to the unusual compatibilization, the thermal properties of the polymer blend are remarkably improved compared with the conventional solvent-cast blend. This method is also applicable to the compatibilization of PSt and polyacrylonitrile, which have very different solubility parameters.

  6. Mixing of immiscible polymers using nanoporous coordination templates.

    PubMed

    Uemura, Takashi; Kaseda, Tetsuya; Sasaki, Yotaro; Inukai, Munehiro; Toriyama, Takaaki; Takahara, Atsushi; Jinnai, Hiroshi; Kitagawa, Susumu

    2015-01-01

    The establishment of methodologies for the mixing of immiscible substances is highly desirable to facilitate the development of fundamental science and materials technology. Herein we describe a new protocol for the compatibilization of immiscible polymers at the molecular level using porous coordination polymers (PCPs) as removable templates. In this process, the typical immiscible polymer pair of polystyrene (PSt) and poly(methyl methacrylate) (PMMA) was prepared via the successive homopolymerizations of their monomers in a PCP to distribute the polymers inside the PCP particles. Subsequent dissolution of the PCP frameworks in a chelator solution affords a PSt/PMMA blend that is homogeneous in the range of several nanometers. Due to the unusual compatibilization, the thermal properties of the polymer blend are remarkably improved compared with the conventional solvent-cast blend. This method is also applicable to the compatibilization of PSt and polyacrylonitrile, which have very different solubility parameters.

  7. A Zn based coordination polymer exhibiting long-lasting phosphorescence.

    PubMed

    Cepeda, Javier; Sebastian, Eider San; Padro, Daniel; Rodríguez-Diéguez, Antonio; García, Jose A; Ugalde, Jesus M; Seco, Jose M

    2016-07-01

    A new Zn(ii) based coordination polymer (CP) built by the cohesive pilling of 2D Shubnikov type layers is reported. This material exhibits time dependent multicoloured emission, part of which shows a persistent green phosphorescence visible for up to two seconds to the naked eye, which originates from multiple charge transfer mechanisms. PMID:27297330

  8. Zinc oxide nano- and microfabrication from coordination-polymer templates.

    PubMed

    Liu, Xiaogang

    2009-01-01

    Hex nut: An emerging synthetic approach based on metal-organic coordination-polymer templates has been used to fabricate micro- and nanoscale crystals. By using a diverse range of molecular building blocks coupled with conventional synthetic techniques, it is possible to synthesize ZnO crystals with tailored sizes, shapes (such as hexagonal rings; see figure), and surface properties.

  9. Rendering non-energetic microporous coordination polymers explosive.

    PubMed

    McDonald, Kyle A; Bennion, Jonathan C; Leone, Amanda K; Matzger, Adam J

    2016-09-18

    Adsorption of oxidizing guest molecules into a non-energetic microporous coordination polymer produces explosives with desirable oxygen balance, high heat released upon decomposition, and suppressed vapor pressure of the guest. Here, this results in primary explosives, materials very sensitive to impact, that have the potential to be used as replacements for lead-based initiators.

  10. A new redox-active coordination polymer with cobalticinium dicarboxylate.

    PubMed

    Kondo, Mitsuru; Hayakawa, Yuri; Miyazawa, Makoto; Oyama, Aiko; Unoura, Kei; Kawaguchi, Hiroyuki; Naito, Tetsuyoshi; Maeda, Kenji; Uchida, Fumio

    2004-09-20

    A new two-dimensional coordination polymer with cobalticinium 1,1'-dicarboxylate (ccdc) incorporated in the framework has been prepared, the ccdc functioning as unique monoanionic dicarboxylate ligands. The compound shows a high redox activity based on the ccdc units.

  11. Coordination polymer particles as potential drug delivery systems.

    PubMed

    Imaz, Inhar; Rubio-Martínez, Marta; García-Fernández, Lorena; García, Francisca; Ruiz-Molina, Daniel; Hernando, Jordi; Puntes, Victor; Maspoch, Daniel

    2010-07-14

    Micro- and nanoscale coordination polymer particles can be used for encapsulating and delivering drugs. In vitro cancer cell cytotoxicity assays showed that these capsules readily release doxorubicin, which shows anticancer efficacy. The results from this work open up new avenues for metal-organic capsules to be used as potential drug delivery systems.

  12. Strategies, linkers and coordination polymers for high-performance sorbents

    SciTech Connect

    Matzger, Adam J.; Wong-Foy, Antek G.; Lebel, Oliver

    2015-09-15

    A linking ligand compound includes three bidentate chemical moieties distributed about a central chemical moiety. Another linking ligand compound includes a bidentate linking ligand and a monodentate chemical moiety. Coordination polymers include a plurality of metal clusters linked together by residues of the linking ligand compounds.

  13. Coordination polymer particles as potential drug delivery systems.

    PubMed

    Imaz, Inhar; Rubio-Martínez, Marta; García-Fernández, Lorena; García, Francisca; Ruiz-Molina, Daniel; Hernando, Jordi; Puntes, Victor; Maspoch, Daniel

    2010-07-14

    Micro- and nanoscale coordination polymer particles can be used for encapsulating and delivering drugs. In vitro cancer cell cytotoxicity assays showed that these capsules readily release doxorubicin, which shows anticancer efficacy. The results from this work open up new avenues for metal-organic capsules to be used as potential drug delivery systems. PMID:20485835

  14. Rendering non-energetic microporous coordination polymers explosive.

    PubMed

    McDonald, Kyle A; Bennion, Jonathan C; Leone, Amanda K; Matzger, Adam J

    2016-09-18

    Adsorption of oxidizing guest molecules into a non-energetic microporous coordination polymer produces explosives with desirable oxygen balance, high heat released upon decomposition, and suppressed vapor pressure of the guest. Here, this results in primary explosives, materials very sensitive to impact, that have the potential to be used as replacements for lead-based initiators. PMID:27523573

  15. Unusual Transformation from a Solvent-Stabilized 1D Coordination Polymer to a Metal-Organic Framework (MOF)-Like Cross-Linked 3D Coordination Polymer.

    PubMed

    Lee, Seung-Chul; Choi, Eun-Young; Lee, Sang-Beom; Kim, Sang-Wook; Kwon, O-Pil

    2015-10-26

    An unusual 1D-to-3D transformation of a coordination polymer based on organic linkers containing highly polar push-pull π-conjugated side chains is reported. The coordination polymers are synthesized from zinc nitrate and an organic linker, namely, 2,5-bis{4-[1-(4-nitrophenyl)pyrrolidin-2-yl]butoxy}terephthalic acid, which possesses highly polar (4-nitrophenyl)pyrrolidine groups, with high dipole moments of about 7 D. The coordination polymers exhibit an unusual transformation from a soluble, solvent-stabilized 1D coordination polymer into an insoluble, metal-organic framework (MOF)-like 3D coordination polymer. The coordination polymer exhibits good film-forming ability, and the MOF-like films are insoluble in conventional organic solvents.

  16. Lanthanide coordination polymers: Synthesis, diverse structure and luminescence properties

    SciTech Connect

    Song, Xue-Qin Lei, Yao-Kun; Wang, Xiao-Run; Zhao, Meng-Meng; Peng, Yun-Qiao; Cheng, Guo-Quan

    2014-10-15

    The new semirigid exo-bidentate ligand incorporating furfurysalicylamide terminal groups, namely, 1,4-bis([(2′-furfurylaminoformyl)phenoxyl]methyl)-2,5-bismethylbenzene (L) was synthesized and used as building blocks for constructing lanthanide coordination polymers with luminescent properties. The series of lanthanide nitrate complexes have been characterized by elemental analysis, IR spectroscopy, and X-ray diffraction analysis. The semirigid ligand L, as a bridging ligand, reacts with lanthanide nitrates forming three distinct structure types: chiral noninterpenetrated two-dimensional (2D) honeycomblike (6,3) (hcb, Schläfli symbol 6{sup 3}, vertex symbol 6 6 6) topological network as type I, 1D zigzag chain as type II and 1D trapezoid ladder-like chain as type III. The structural diversities indicate that lanthanide contraction effect played significant roles in the structural self-assembled process. The luminescent properties of Eu{sup III}, Tb{sup III} and Dy{sup III} complexes are discussed in detail. Due to the good match between the lowest triplet state of the ligand and the resonant energy level of the lanthanide ion, the lanthanide ions in Eu{sup III}, Tb{sup III} and Dy{sup III} complexes can be efficiently sensitized by the ligand. - Graphical abstract: We present herein six lanthanide coordination polymers of a new semirigid exo-bidentate ligand which not only display diverse structures but also possess strong luminescence properties. - Highlights: • We present lanthanide coordination polymers of a new semirigid exo-bidentate ligand. • The lanthanide coordination polymers exhibit diverse structures. • The luminescent properties of Tb{sup III}, Eu{sup III} and Dy{sup III} complexes are discussed in detail.

  17. Arene Selectivity by a Flexible Coordination Polymer Host.

    PubMed

    Wright, James S; Vitórica-Yrezábal, Iñigo J; Thompson, Stephen P; Brammer, Lee

    2016-09-01

    The coordination polymers [Ag4 (O2 CCF3 )4 (phen)3 ]⋅ phen⋅arene (1⋅phen⋅arene) (phen=phenazine; arene=toluene, p-xylene or benzene) have been synthesised from the solution phase in a series of arene solvents and crystallographically characterised. By contrast, analogous syntheses from o-xylene and m-xylene as the solvent yield the solvent-free coordination polymer [Ag4 (O2 CCF3 )4 (phen)2 ] (2). Toluene, p-xylene and benzene have been successfully used in mixed-arene syntheses to template the formation of coordination polymers 1⋅phen⋅arene, which incorporate o- or m-xylene. The selectivity of 1⋅phen⋅arene for the arene guests was determined, through pairwise competition experiments, to be p-xylene>toluene≈benzene>o-xylene>m-xylene. The largest selectivity coefficient was determined as 14.2 for p-xylene:m-xylene and the smallest was 1.0 for toluene:benzene. PMID:27483388

  18. Arene Selectivity by a Flexible Coordination Polymer Host.

    PubMed

    Wright, James S; Vitórica-Yrezábal, Iñigo J; Thompson, Stephen P; Brammer, Lee

    2016-09-01

    The coordination polymers [Ag4 (O2 CCF3 )4 (phen)3 ]⋅ phen⋅arene (1⋅phen⋅arene) (phen=phenazine; arene=toluene, p-xylene or benzene) have been synthesised from the solution phase in a series of arene solvents and crystallographically characterised. By contrast, analogous syntheses from o-xylene and m-xylene as the solvent yield the solvent-free coordination polymer [Ag4 (O2 CCF3 )4 (phen)2 ] (2). Toluene, p-xylene and benzene have been successfully used in mixed-arene syntheses to template the formation of coordination polymers 1⋅phen⋅arene, which incorporate o- or m-xylene. The selectivity of 1⋅phen⋅arene for the arene guests was determined, through pairwise competition experiments, to be p-xylene>toluene≈benzene>o-xylene>m-xylene. The largest selectivity coefficient was determined as 14.2 for p-xylene:m-xylene and the smallest was 1.0 for toluene:benzene.

  19. Stability of complex coacervate core micelles containing metal coordination polymer.

    PubMed

    Yan, Yun; de Keizer, Arie; Cohen Stuart, Martien A; Drechsler, Markus; Besseling, Nicolaas A M

    2008-09-01

    We report on the stability of complex coacervate core micelles, i.e., C3Ms (or PIC, BIC micelles), containing metal coordination polymers. In aqueous solutions these micelles are formed between charged-neutral diblock copolymers and oppositely charged coordination polymers formed from metal ions and bisligand molecules. The influence of added salt, polymer concentration, and charge composition was investigated by using light scattering and cryo-TEM techniques. The scattering intensity decreases strongly with increasing salt concentration until a critical salt concentration beyond which no micelles exist. The critical micelle concentration increases almost exponentially with the salt concentration. From the scattering results it follows that the aggregation number decreases with the square root of the salt concentration, but the hydrodynamic radius remains constant or increases slightly. It was concluded that the density of the core decreases with increasing ionic strength. This is in agreement with theoretical predictions and is also confirmed by cryo-TEM measurements. A complete composition diagram was constructed based on the composition boundaries obtained from light scattering titrations.

  20. Designer coordination polymers: dimensional crossover architectures and proton conduction.

    PubMed

    Yamada, Teppei; Otsubo, Kazuya; Makiura, Rie; Kitagawa, Hiroshi

    2013-08-21

    Coordination polymers (CPs) have large degrees of freedom in framework compositions and in the structures and environment of the inner pores. This review focuses on the recent significant progress achieved by controlling these degrees of freedom. Two breakthroughs are reviewed for constructing sophisticated structures of CP frameworks, especially in dimensional crossover regions. The first is the synthesis of quasi one-dimensional halogen-bridged coordinative tubes by applying state-of-the-art techniques of coordination chemistry. The electronic state of the coordinative tube was studied by structural, spectroscopic and theoretical methods and found to be distinct from conventional one-dimensional systems. The second breakthrough is the achievement of a quasi-two-dimensional architecture by combining Langmuir-Blodgett and layer-by-layer methods. Two-dimensional LB CP films were prepared on liquid; the films were stacked layer by layer, and a crystalline quasi-two-dimensional structure was constructed. This review also covers the design of the environment of the inner pore, where hydrogen bond networks with various acidic sites were modified. By appropriate design of the hydrogen bond network, proton-conductive CPs are invented, which are summarized in this review. Types of proton donor sites are discussed and classified, and superprotonic conductive CPs were achieved in these investigations. These results will provide new strategies for constructing functional materials for smart devices.

  1. Complex coacervate core micelles from iron-based coordination polymers.

    PubMed

    Wang, Junyou; de Keizer, Arie; Fokkink, Remco; Yan, Yun; Cohen Stuart, Martien A; van der Gucht, Jasper

    2010-07-01

    Complex coacervate core micelles (C3Ms) from cationic poly(N-methyl-2-vinyl-pyridinium iodide)-b-poly(ethylene oxide) (P2MVP(41)-b-PEO(205)) and anionic iron coordination polymers are investigated in the present work. Micelle formation is studied by light scattering for both Fe(II)- and Fe(III)-containing C3Ms. At the stoichiometric charge ratio, both Fe(II)-C3Ms and Fe(III)-C3Ms are stable for at least 1 week at room temperature. Excess of iron coordination polymers has almost no effect on the formed Fe(II)-C3Ms and Fe(III)-C3Ms, whereas excess of P2MVP(41)-b-PEO(205) copolymers in the solution can dissociate the formed micelles. Upon increasing salt concentration, the scattering intensity decreases. This decrease is due to both a decrease in the number of micelles (or an increase in CMC) and a decrease in aggregation number. The salt dependence of the CMC and the aggregation number is explained using a scaling argument for C3M formation. Compared with Fe(II)-C3Ms, Fe(III)-C3Ms have a lower CMC and a higher stability against dissociation by added salt.

  2. Hydrogen bonding and multiphonon structure in copper pyrazine coordination polymers.

    PubMed

    Brown, S; Cao, J; Musfeldt, J L; Conner, M M; McConnell, A C; Southerland, H I; Manson, J L; Schlueter, J A; Phillips, M D; Turnbull, M M; Landee, C P

    2007-10-15

    We report a systematic investigation of the temperature-dependent infrared vibrational spectra of a family of chemically related coordination polymer magnets based upon bridging bifluoride (HF(2)-) and terminal fluoride (F-) ligands in copper pyrazine complexes including Cu(HF(2))(pyz)(2)BF(4), Cu(HF(2))(pyz)(2)ClO(4), and CuF(2)(H(2)O)(2)(pyz). We compare our results with several one- and two-dimensional prototype materials including Cu(pyz)(NO(3))(2) and Cu(pyz)(2)(ClO(4))(2). Unusual low-temperature hydrogen bonding, local structural transitions associated with stronger low-temperature hydrogen bonding, and striking multiphonon effects that derive from coupling of an infrared-active fundamental with strong Raman-active modes of the pyrazine building-block molecule are observed. On the basis of the spectroscopic evidence, these interactions are ubiquitous to this family of coordination polymers and may work to stabilize long-range magnetic ordering at low temperature. Similar interactions are likely to be present in other molecule-based magnets.

  3. Magnetic Iron Oxide Nanoparticle Seeded Growth of Nucleotide Coordinated Polymers.

    PubMed

    Liang, Hao; Liu, Biwu; Yuan, Qipeng; Liu, Juewen

    2016-06-22

    The introduction of functional molecules to the surface of magnetic iron oxide nanoparticles (NPs) is of critical importance. Most previously reported methods were focused on surface ligand attachment either by physisorption or covalent conjugation, resulting in limited ligand loading capacity. In this work, we report the seeded growth of a nucleotide coordinated polymer shell, which can be considered as a special form of adsorption by forming a complete shell. Among all of the tested metal ions, Fe(3+) is the most efficient for this seeded growth. A diverse range of guest molecules, including small organic dyes, proteins, DNA, and gold NPs, can be encapsulated in the shell. All of these molecules were loaded at a much higher capacity compared to that on the naked iron oxide NP core, confirming the advantage of the coordination polymer (CP) shell. In addition, the CP shell provides better guest protein stability compared to that of simple physisorption while retaining guest activity as confirmed by the entrapped glucose oxidase assay. Use of this system as a peroxidase nanozyme and glucose biosensor was demonstrated, detecting glucose as low as 1.4 μM with excellent stability. This work describes a new way to functionalize inorganic materials with a biocompatible shell. PMID:27248668

  4. A Lamellar Coordination Polymer with Remarkable Catalytic Activity.

    PubMed

    Mendes, Ricardo F; Antunes, Margarida M; Silva, Patrícia; Barbosa, Paula; Figueiredo, Filipe; Linden, Anthony; Rocha, João; Valente, Anabela A; Almeida Paz, Filipe A

    2016-09-01

    A positively charged lamellar coordination polymer based on a flexible triphosphonic acid linker is reported. [Gd(H4 nmp)(H2 O)2 ]Cl⋅2 H2 O (1) [H6 nmp=nitrilotris(methylenephosphonic acid)] was obtained by a one-pot approach by using water as a green solvent and by forcing the inclusion of additional acid sites by employing HCl in the synthesis. Compound 1 acts as a versatile heterogeneous acid catalyst with outstanding activity in organic reactions such as alcoholysis of styrene oxide, acetalization of benzaldehyde and cyclohexanaldehyde and ketalization of cyclohexanone. For all reaction systems, very high conversions were reached (92-97 %) in only 15-30 min under mild conditions (35 °C, atmospheric pressure). The coordination polymer exhibits a protonic conductivity of 1.23×10(-5)  S cm(-1) at 98 % relative humidity and 40 °C. PMID:27505712

  5. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    PubMed

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

  6. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    PubMed

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here. PMID:26687811

  7. New 4,5-dichlorophthalhydrazidate-bridged chained coordination polymers

    SciTech Connect

    Jin, Juan; Wu, Di; Jia, Ming-Jun; Peng, Yu; Yu, Jie-Hui; Wang, Yu-Chang; Xu, Ji-Qing

    2011-03-15

    The hydrothermal self-assemblies of Pb{sup 2+}/Cd{sup 2+} salt, 4,5-dichlorophthalic acid (dcpha), N{sub 2}H{sub 4}.H{sub 2}O together with 1,10-phenanthroline.H{sub 2}O (phen) or 2,2'-bipyridine (bpy) generated two new monoacylhydrazidate-bridged 1-D chained coordination polymers [Pb{sub 2}(DCPTH){sub 4}(phen){sub 2}] 1 and [Cd{sub 3}(DCPTH){sub 2}(dcph){sub 2}(bpy){sub 2}] 2 (DCPTH=4,5-dichlorophthalhydrazidate, dcph=4,5-dichlorophthalate). The monoacylhydrazidate ligand DCPTH originated from the hydrothermal in situ acylation reaction between dcpha and N{sub 2}H{sub 4}.H{sub 2}O. In compound 1, two types of coordination modes for DCPTH are found, which link alternately the Pb(II) centers into a 1-D chain structure of compound 1 with ancillary phen molecules. In compound 2, DCPTH and dcph as the mixed bridges extend the Cd(II) centers into a 1-D chain structure of compound 2 with auxiliary bpy molecules. DCPTH in compound 2 shows a different coordination mode from those observed in compound 1. -- Graphical abstract: By applying the in situ acylation reaction between 4,5-diclorophthalic acid and N{sub 2}H{sub 4}.H{sub 2}O, two 4,5-dichlorophthalhydrazidate-bridged chained compounds [Pb{sub 2}(DCPTH){sub 4}(phen){sub 2}] and [Cd{sub 3}(DCPTH){sub 2}(dcph){sub 2}(bpy){sub 2}] (4,5-dichlorophthalhydrazidate=DCPTH, and dcph=4,5-dichlorophthalate) were hydrothermally synthesized. Display Omitted Research highlights: > In this article, we first reported the preparations and structural characterization of two examples of 4,5-dichlorophthalhydrazidate-bridged chained coordination polymers [Pb{sub 2}(DCPTH){sub 4}(phen){sub 2}] 1 and [Cd{sub 3}(DCPTH){sub 2}(dcph){sub 2}(bpy){sub 2}] 2. 4,5-dichlorophthalhydrazidate derived from the hydrothermal in situ acylation reactions between 4,5-dichlorophthalic acid and N{sub 2}H{sub 4}.H{sub 2}O. > In this article, a simple method to judge whether the polycarboxylic acid precursors have acylated into the acylhydrazidate ligands is

  8. A three-dimensional microporous coordination polymer with fluorescent property

    NASA Astrophysics Data System (ADS)

    Gao, Chaoying; Liu, Shuxia; Xie, Linhua; Ren, Yuanhang; Cao, Ruige; Cao, Jianfang; Zhao, Xinyu

    2008-11-01

    A microporous metal-organic coordination polymer formulated as [Cd 2(btec)(H 2O) 2]·0.8DMF (1), where btec = 1,2,4,5-benzenetetracarboxylate and DMF = N, N-dimethylformamide, has been isolated under solvothermal condition and characterized by elemental analyses, IR, thermal stability analysis, fluorescent spectrum, and single-crystal X-ray diffraction analysis. The framework in 1 possesses a three-dimensional architecture with ordered one-dimensional rhombus channels, the dimensions of channels are approximately 10 Å at the widest and 3 Å at the narrowest spacing considering the van der Waal radii of atoms in the framework running along the a-axis. Furthermore, compound 1 shows intense photoluminescent property at room temperature.

  9. A coordination polymer nanobelt (CPNB)-based aptasensor for sulfadimethoxine.

    PubMed

    Song, Kyung-Mi; Jeong, Euiyoung; Jeon, Weejeong; Jo, Hunho; Ban, Changill

    2012-03-15

    A polymer-based aptasensor, which consisted of fluorescein amidite (FAM)-modified aptamers and coordination polymer nanobelts (CPNBs), was developed utilizing the fluorescence quenching effect to detect sulfadimethoxine residue in food products. A single-stranded DNA (ssDNA) aptamer, which was a specific bio-probe for sulfadimethoxine (Su13; 5'-GAGGGCAACGAGTGTTTATAGA-3'), was discovered by a magnetic bead-based systematic evolution of ligands by exponential enrichment (SELEX) technique, and the fluorescent quenchers CPNBs were produced by mixing AgNO(3) and 4,4'-bipyridine. This aptasensor easily and sensitively detected sulfadimethoxine in solution with a limit of detection (LOD) of 10ng/mL. Furthermore, the antibiotic dissolved in milk was also effectively detected with the same LOD value. In addition, this aptamer probe offered high specificity for sulfadimethoxine compared to other antibiotics. These valuable results provide ample evidence that the CPNB-based aptasensor can be used to quantify sulfadimethoxine residue in food products. PMID:22244734

  10. Nanoscale coordination polymers exhibiting luminescence properties and NMR relaxivity.

    PubMed

    Chelebaeva, Elena; Larionova, Joulia; Guari, Yannick; Ferreira, Rute A S; Carlos, Luis D; Trifonov, Alexander A; Kalaivani, Thangavel; Lascialfari, Alessandro; Guérin, Christian; Molvinger, Karine; Datas, Lucien; Maynadier, Marie; Gary-Bobo, Magali; Garcia, Marcel

    2011-03-01

    This article presents the first example of ultra-small (3-4 nm) magneto-luminescent cyano-bridged coordination polymer nanoparticles Ln0.33(3+)Gdx3+/[Mo(CN)8]3- (Ln=Eu (x=0.34), Tb (x=0.35)) enwrapped by a natural biocompatible polymer chitosan. The aqueous colloidal solutions of these nanoparticles present a luminescence characteristic of the corresponding lanthanides (5D0→7F0-4 (Eu3+) or the 5D4→7F6-2 (Tb3+)) under UV excitation and a green luminescence of the chitosan shell under excitation in the visible region. Magnetic Resonance Imaging (MRI) efficiency, i.e. the nuclear relaxivity, measurements performed for Ln0.33(3+)Gdx3+/[Mo(CN)8]3- nanoparticles show r1p and r2p relaxivities slightly higher than or comparable to the ones of the commercial paramagnetic compounds Gd-DTPA® or Omniscan® indicating that our samples may potentially be considered as a positive contrast agent for MRI. The in vitro studies performed on these nanoparticles show that they maybe internalized into human cancer and normal cells and well detected by fluorescence at the single cell level. They present high stability even at low pH and lack of cytotoxicity both in human cancer and normal cells.

  11. Two new coordination polymers, a trinuclear metal complex and their interconversion depending on the solvent.

    PubMed

    Koike, Shiori; Hirakawa, Takeshi; Yamanishi, Katsunori; Kondo, Mitsuru

    2014-09-14

    Two new 1-D coordination polymers and a discrete trinuclear complex with a double-ring framework were synthesized and structurally characterized. The unique irreversible conversion from one of the 1-D coordination polymers to the trinuclear complex by contact with MeCN is described.

  12. Structural Design Parameters for Highly Birefringent Coordination Polymers.

    PubMed

    Thompson, John R; Katz, Michael J; Williams, Vance E; Leznoff, Daniel B

    2015-07-01

    A series of coordination polymer materials incorporating the highly anisotropic 2-(2-pyridyl)-1,10-phenanthroline (phenpy) building block have been synthesized and structurally characterized. M(phenpy)[Au(CN)2]2 (M = Cd, Mn) are isostructural and form a 1-D chain through bridging [Au(CN)2](-) units and extend into a 2-D sheet through aurophilic interactions. M(phenpy)(H2O)[Au(CN)2]2·2H2O (M = Cd, Mn, and Zn) are also isostructural but differ from the first set via the inclusion of a water molecule into the coordination sphere, resulting in a 1-D topology through aurophilic interactions. In(phenpy)(Cl)2[Au(CN)2]·0.5H2O forms a dimer through bridging chlorides and contains a free [Au(CN)2](-) unit. In the plane of the primary crystal growth direction, the birefringence values (Δn) of 0.37(2) (Cd(phenpy)[Au(CN)2]2), 0.50(3) (In(phenpy)(Cl)2[Au(CN)2]·0.5H2O), 0.56(3) and 0.59(6) (M(phenpy)(H2O)[Au(CN)2]2·2H2O M = Cd and Zn, respectively) were determined. β, a structural parameter defined by phenpy units rotated in the A-C plane relative to the light propagation (C) direction, was found to correlate to Δn magnitudes. The addition of a carbon-carbon double bond to terpy has increased the molecular polarizability anisotropy of the building block, and all structures have reduced deviation from planarity in comparison to terpy and terpy derivative structures, leading to these higher Δn values, which are among the highest reported for crystalline solids. PMID:26098267

  13. Polymer complexes. LX. Supramolecular coordination and structures of N(4-(acrylamido)-2-hydroxybenzoic acid) polymer complexes

    NASA Astrophysics Data System (ADS)

    Ghoneim, M. M.; El-Sonbati, A. Z.; El-Bindary, A. A.; Diab, M. A.; Serag, L. S.

    2015-04-01

    A number of novel polymer complexes of various anions of copper(II), cobalt(II), nickel(II) and uranyl(II) with N(4-(acrylamido)-2-hydroxy benzoic acid) (ABH) have been synthesized and characterized by elemental analysis, IR, 1H NMR, magnetic susceptibility measurements, electronic spin resonance, vibrational spectra and thermal analysis. The molecular structures of the ligand are optimized theoretically and the quantum chemical parameters are calculated. Tentative structures for the polymeric metal complexes due to their potential application are also suggested. The IR data exhibit the coordination of ONO2/OAc/SO4 with the metal ions in the polymeric metal complex. Vibrational spectra indicate coordination of carboxylate oxygen and phenolic OH of the ligand giving a MO4 square planar chromophore. Ligand field ESR spectra support square planar geometry around Cu(II). The thermal decomposition of the polymer complexes were discussed in relation to structure, and the thermodynamic parameters of the decomposition stages were evaluated applying Coast-Redfern and Horowitz-Metzger methods.

  14. Carbon dioxide (CO2) absorption behavior of mixed matrix polymer composites containing a flexible coordination polymer.

    PubMed

    Culp, Jeffrey T; Sui, Lang; Goodman, Angela; Luebke, David

    2013-03-01

    Mixed matrix membranes (MMMs) comprised of metal organic frameworks (MOFs) dispersed in organic polymers are popular materials under study for potential applications in gas separations. However, research on MMMs containing structurally dynamic sorbents known as flexible MOFs has only very recently appeared in the literature. The thermodynamic requirements of the structure transition between the low porosity and high porosity phases of flexible MOFs may provide a mechanism for high adsorption selectivity in these materials. A fundamental question in MMMs containing flexible MOFs is how the constraint of the polymer matrix on the intrinsic expansion of the flexible MOF particles that occurs during gas adsorption might affect the thermodynamics of this structural phase transition and influence the gas adsorption properties of the embedded MOF. To investigate the fundamental nature of this flexible MOF-polymer interface, thin films of ~20 um thickness were prepared using the flexible linear chain coordination polymer catena-bis(dibenzoylmethanato)-(4,4'bipyridyl)nickel(II) "Ni(Bpy)(DBM)(2)" embedded as 35 wt% dispersions in Matrimid®, polystyrene, and polysulfone. The adsorption of CO(2) in the polymers and embedded particles was studied using in situ ATR-FTIR spectroscopy and variable temperature volumetric CO(2) adsorption/desorption isotherms. Interestingly, no effect of the polymer matrix on the gas adsorption behavior of the embedded Ni(Bpy)(DBM)(2) particles was observed. The composite samples all showed the same threshold pressures for CO(2) absorption and desorption hysteresis associated with the structural phase change in the polymer embedded Ni(Bpy)(DBM)(2) particles as was observed in the pristine polycrystalline sample. The current results contrast those recently reported for a MMM containing the flexible MOF "NH(2)-MIL-53" where a significant increase in the threshold pressure for CO(2) adsorption associated with the structural phase change of the MOF was

  15. Nanoscale coordination polymers for platinum-based anticancer drug delivery.

    PubMed

    Rieter, William J; Pott, Kimberly M; Taylor, Kathryn M L; Lin, Wenbin

    2008-09-01

    Pt-containing nanoscale coordination polymer (NCP) particles with the formula of Tb2(DSCP)3(H2O)12 (where DSCP represents disuccinatocisplatin), NCP-1, were precipitated from an aqueous solution of Tb3+ ions and DSCP bridging ligands via the addition of a poor solvent. SEM and TEM images showed that as-synthesized NCP-1 exhibited a spherical morphology with a DLS diameter of 58.3 +/- 11.3 nm. NCP-1 particles were stabilized against rapid dissolution in water by encapsulation in shells of amorphous silica. The resulting silica-coated particles NCP-1' exhibited significantly longer half-lives for DSCP release from the particles (a t1/2 of 9 h for NCP-1' with 7 nm silica coating vs t1/2 of 1 h for as-synthesized NCP-1). In vitro cancer cell cytotoxicity assays with the human colon carcinoma cell line (HT-29) showed that internalized NCP-1' particles readily released the DSCP moieties which were presumably reduced to cytotoxic Pt(II) species to give the Pt-containing NCPs anticancer efficacy superior to the cisplatin standard. The generality of this degradable nanoparticle formulation should allow for the design of NCPs as effective delivery vehicles for a variety of biologically and medically important cargoes such as therapeutic and imaging agents.

  16. Soluble porous coordination polymers by mechanochemistry: from metal-containing films/membranes to active catalysts for aerobic oxidation.

    PubMed

    Zhang, Pengfei; Li, Haiying; Veith, Gabriel M; Dai, Sheng

    2015-01-14

    Soluble porous coordination polymers from mechanochemical synthesis are presented through a coordination polymerization between highly contorted, rigid tetraphenol and a broad variety of transition metal ions. These polymers can be easily cast as metal-containing films or freestanding membranes. Importantly, as-made coordination polymers are highly active and stable in the aerobic oxidation of allylic C-H bonds. PMID:25389070

  17. Different geometrical arrangements in carboxylate coordination polymers of flexible dicarboxylic acid

    SciTech Connect

    Deka, Himangshu; Sarma, Rupam; Kumari, Satchi; Khare, Alika; Baruah, Jubaraj B.

    2011-07-15

    Dicarboxylate coordination polymers (1-5) of Mn(II), Ni(II), Cu(II), Zn(II) and Cd(II), respectively, derived from (7-carboxymethoxy-naphthalen-2-yloxy)-acetic acid (L{sub 1}H{sub 2}) are synthesized and characterized. Depending on the coordination sites around the metal centers and coordination mode of the ligand, dimensionality of these polymers varies. The dicarboxylates adopt three spatial orientations: in-plane linear coordination, out-of-plane cis coordination and out-of-plane trans coordination mode. Both the cis and trans out-of-plane coordination modes are found to exist only if the ancillary ligand pyridine is coordinated to the metal ion. When the aquoligand coordinates the in-plane linear coordination mode of L{sub 1} predominates. The coordination polymers 4 and 5 show photoluminescence in solution. The dicarboxylate of (5-carboxymethoxy-naphthalen-1-yloxy)-acetic acid (L{sub 2}H{sub 2}) does not form coordination polymer under ambient conditions, but prefers to remain as uncoordinated anion providing hydrophobic confinement to hexa-aquometal(II) cation. Compound 3 crystallizes in P2{sub 1} space group and it shows broadband ultra-violet fluorescence centered at 352.9 nm on focusing 632.8 nm He:Ne laser. - Graphical abstract: Different geometrical arrangements in coordination polymers derived from (7-carboxymethoxy-naphthalen-2-yloxy)-acetic acid of metal ions Mn(II), Ni(II), Cu(II), Zn(II) and Cd(II) are presented. The (5-carboxymethoxy-naphthalen-1-yloxy)-acetic acid led to hexa-aquo cadmium(II) dicarboxylate. Highlights: > Structural and spectroscopic characterizations of five dicarboxylate coordination polymers of (7-carboxymethoxy-naphthalen-2-yloxy)-acetic acid with different metal ions are presented. > Different geometrical arrangements of coordination polymers stabilized in solid state are described. > Photoluminescence properties of the polymers are shown. > NLO property of a copper coordination polymer is described.

  18. Mesoporous graphitic carbon nanodisks fabricated via catalytic carbonization of coordination polymers.

    PubMed

    Su, Panpan; Jiang, Liang; Zhao, Jiao; Yan, Jingwang; Li, Can; Yang, Qihua

    2012-09-11

    Mesoporous graphitic carbon nanodisks with hierarchical porous structure, facilely fabricated by catalytic carbonization of iron-based coordination polymer nanodisks, exhibit high capacitance even at high scan rates as electrode materials for electrochemical double layer capacitors.

  19. Linking homogeneous and heterogeneous enantioselective catalysis through a self-assembled coordination polymer.

    PubMed

    García, José I; López-Sánchez, Beatriz; Mayoral, José A

    2008-11-01

    Combining the advantages of homogeneous and heterogeneous enantioselective catalysis is possible through self-supported copper coordination polymers, based on a new kind of ditopic chiral ligand bearing two azabis(oxazoline) moieties. When the coordination polymer is used to catalyze a cyclopropanation reaction, it becomes soluble in reaction conditions but precipitates after reaction completion, allowing easy recovery and efficient reuse in the same reaction up to 14 times.

  20. Bis(oxazoline)-based coordination polymers: a recoverable system for enantioselective Henry reactions.

    PubMed

    Angulo, Beatriz; García, José I; Herrerías, Clara I; Mayoral, José A; Miñana, Ana C

    2012-07-01

    An efficient release-capture strategy for the recovery and reuse of enantioselective catalysts in the Henry reaction is described. This strategy is based on the precipitation of an insoluble coordination polymer at the end of each reaction, allowing easy separation from products. The coordination polymer is formed through aggregation of Cu(II) ions with ditopic bisoxazoline-based chiral ligands. Up to 11 catalytic cycles have been conducted keeping good yields and enantioselectivities.

  1. Lanthanide(III) complexation with an amide derived pyridinophane.

    PubMed

    Castro, Goretti; Bastida, Rufina; Macías, Alejandro; Pérez-Lourido, Paulo; Platas-Iglesias, Carlos; Valencia, Laura

    2015-02-16

    Herein we report a detailed investigation of the solid state and solution structures of lanthanide(III) complexes with the 18-membered pyridinophane ligand containing acetamide pendant arms TPPTAM (TPPTAM = 2,2',2″-(3,7,11-triaza-1,5,9(2,6)-tripyridinacyclododecaphane-3,7,11-triyl)triacetamide). The ligand crystallizes in the form of a clathrated hydrate, where the clathrated water molecule establishes hydrogen-bonding interactions with the amide NH groups and two N atoms of the macrocycle. The X-ray structures of 13 different Ln(3+) complexes obtained as the nitrate salts (Ln(3+) = La(3+)-Yb(3+), except Pm(3+)) have been determined. Additionally, the X-ray structure of the La(3+) complex obtained as the triflate salt was also obtained. In all cases the ligand provides 9-fold coordination to the Ln(3+) ion, ten coordination being completed by an oxygen atom of a coordinated water molecule or a nitrate or triflate anion. The bond distances of the metal coordination environment show a quadratic change along the lanthanide series, as expected for isostructural series of Ln(3+) complexes. Luminescence lifetime measurements obtained from solutions of the Eu(3+) and Tb(3+) complexes in H2O and D2O point to the presence of a water molecule coordinated to the metal ion in aqueous solutions. The analysis of the Ln(3+)-induced paramagnetic shifts indicates that the complexes are ten-coordinated throughout the lanthanide series from Ce(3+) to Yb(3+), and that the solution structure is very similar to the structures observed in the solid state. The complexes of the light Ln(3+) ions are fluxional due to a fast Δ(λλλλλλ) ↔ Λ(δδδδδδ) interconversion that involves the inversion of the macrocyclic ligand and the rotation of the acetamide pendant arms. The complexes of the small Ln(3+) ions are considerably more rigid, the activation free energy determined from VT (1)H NMR for the Lu(3+) complex being ΔG(⧧)298 = 72.4 ± 5.1 kJ mol(-1).

  2. Determination of tetracycline in milk by using nucleotide/lanthanide coordination polymer-based ternary complex.

    PubMed

    Tan, Hongliang; Ma, Chanjiao; Song, Yonghai; Xu, Fugang; Chen, Shouhui; Wang, Li

    2013-12-15

    The meta-organic coordination polymers have been emerged as fascinating nanomaterials because of their tunable nature. In this work, we employed lanthanide coordination polymer self-assembled from adenosine monophosphate (AMP) and europium ion (Eu(3+)) as receptor reagent and citrate (Cit) as ancillary ligand to construct a fluorescent sensor for the detection of tetracycline (Tc) in milk. The co-coordination of Cit and Tc with Eu(3+) on the surface of the coordination polymer AMP/Eu leads to the formation of ternary complex which emitted strong fluorescence due to the removal of coordinated water molecules and an intramolecular energy transfer from Tc to Eu(3+). The fluorescent intensity of Eu(3+) displayed a good linear response to Tc concentrations in the range of 0.1-20 μM with a detection limit of 60 nM. This method was successfully applied to determine the levels of Tc in milk, which is the first application of coordination polymer as a fluorescent sensor in real sample. Compared with other Eu(3+)-based fluorescent methods for Tc detection, the presented method allows simple, direct analysis of Tc without requiring special reaction media or complicated prepreparation processes. This straightforward strategy could be extended to the preparation of other lanthanide coordination polymer-based fluorescent probes for applications in biosensing, imaging, drug delivery, and so on.

  3. Coordinative nanoporous polymers synthesized with hydrogen-bonded columnar liquid crystals.

    PubMed

    Ishihara, Shinsuke; Furuki, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko; Takeoka, Shinji

    2012-10-01

    In this paper, we report the development of nanoporous polymer which demonstrates the coordination property toward zinc porphyrin. A hydrogen-bonded columnar liquid crystalline precursor composed of a triphenylene template and three equivalent of the surrounding dendric amphiphile bearing a pyridyl head group and a polymerizable aliphatic chain, was covalently fixed by photopolymerization, and then the subsequent selective removal of the template successively resulted in a nanoporous polymer in which the pore wall is modified with pyridyl groups. The nanoporous polymer reflected the conformation of template, and displayed considerable coordination ability of the pyridyl groups towards zinc porphyrin. The coordinative nanoporous polymer is promising as a nano-scaled scaffold for the organization of dyes into functional supramolecular architectures.

  4. A series of Ti(IV)/Ti(III) coordination polymers: Structures and surface photoelectric properties

    NASA Astrophysics Data System (ADS)

    Li, Lei; Zhang, Li; Liu, Dong-Wei; Jin, Jing; Chi, Yu-Xian; Niu, Shu-Yun

    2012-02-01

    Three titanium coordination polymers, {[Ti(SO 4) 2(H 2O)]·0.5bipy·2H 2O} n1, {[Ti1(SO 4) 2(H 2O)]·[Ti2(SO 4) 2(H 2O)]·bipy·5H 2O} n2 and [Ti(tea)] n3 (bipy = 4,4'-bipyridine, H 3tea = triethanolamine) were synthesized and characterized by IR, UV-Vis absorption spectra, TG analysis, X-ray single crystal diffraction and surface photovoltage spectroscopy (SPS). The surface photoelectric properties of titanium coordination polymers were discussed emphatically by the SPS. The results of single crystal diffraction indicate that polymers 1 and 2 possess 1D infinite structure bridged by SO 42- groups and coordinated water molecules and further connected into supramolecular structures by hydrogen bonds. Polymer 3 possesses 2D infinite structure bridged by weak sub-coordinated Ti-O bonds. The results of SPS show that there are obvious photovoltage responses in the range of 300-500 nm, which indicates that they possess photoelectric conversion ability. The SPS of three titanium polymers were analyzed comparatively. It is found that the valence of central metal ions, coordination micro-environment and kinds of coordination atoms influence the results of the SPS. The SPS is associated with UV-Vis absorption spectra.

  5. A series of Ti(IV)/Ti(III) coordination polymers: structures and surface photoelectric properties.

    PubMed

    Li, Lei; Zhang, Li; Liu, Dong-Wei; Jin, Jing; Chi, Yu-Xian; Niu, Shu-Yun

    2012-02-01

    Three titanium coordination polymers, {[Ti(SO(4))(2)(H(2)O)]·0.5bipy·2H(2)O}(n)1, {[Ti1(SO(4))(2)(H(2)O)]·[Ti2(SO(4))(2)(H(2)O)]·bipy·5H(2)O}(n)2 and [Ti(tea)](n)3 (bipy=4,4'-bipyridine, H(3)tea=triethanolamine) were synthesized and characterized by IR, UV-Vis absorption spectra, TG analysis, X-ray single crystal diffraction and surface photovoltage spectroscopy (SPS). The surface photoelectric properties of titanium coordination polymers were discussed emphatically by the SPS. The results of single crystal diffraction indicate that polymers 1 and 2 possess 1D infinite structure bridged by SO(4)(2-) groups and coordinated water molecules and further connected into supramolecular structures by hydrogen bonds. Polymer 3 possesses 2D infinite structure bridged by weak sub-coordinated Ti-O bonds. The results of SPS show that there are obvious photovoltage responses in the range of 300-500 nm, which indicates that they possess photoelectric conversion ability. The SPS of three titanium polymers were analyzed comparatively. It is found that the valence of central metal ions, coordination micro-environment and kinds of coordination atoms influence the results of the SPS. The SPS is associated with UV-Vis absorption spectra.

  6. A multi-functional coordination polymer coexisting spontaneous chirality resolution and weak ferromagnetism

    SciTech Connect

    Li, Xiu-Hua; Zhang, Qi; Hu, Ping

    2014-10-15

    A multifunctional homochiral coordination polymer, [Co(H{sub 2}O)(BDC)(4,4′-BPY)]∙3H{sub 2}O (1) (H{sub 2}BDC=1,2-benzenedicarboxylate and 4,4′-BPY=4,4′-bipyridine), has been successfully isolated from Co(II) ions and mixed ligands (1,2-benzenedicarboxylate and 4,4′-bipyridine). Complex 1, which exhibits spontaneous chirality resolution and weak ferromagnetism, is built by chiral helices interconnected via end-to-end 4,4′-BPY bridges into a two-dimensional (2D) layer structure. - Graphical abstract: A 2D cobalt coordination polymer compound showing spontaneous chirality resolution and weak ferromagnetism. - Highlights: • A new 2D cobalt mix-ligand coordination polymer complex has been synthesized. • The cobalt coordination polymer complex shows spontaneous chirality resolution in solid state. • The cobalt coordination polymer complex displays dominant and weak intrachain ferromagnetic interactions.

  7. Direct synthesis of nanoporous carbon nitride fibers using Al-based porous coordination polymers (Al-PCPs).

    PubMed

    Hu, Ming; Reboul, Julien; Furukawa, Shuhei; Radhakrishnan, Logudurai; Zhang, Yuanjian; Srinivasu, Pavuluri; Iwai, Hideo; Wang, Hongjing; Nemoto, Yoshihiro; Suzuki, Norihiro; Kitagawa, Susumu; Yamauchi, Yusuke

    2011-07-28

    We report a new synthetic route for preparation of nanoporous carbon nitride fibers with graphitic carbon nitride polymers, by calcination of Al-based porous coordination polymers (Al-PCPs) with dicyandiamide (DCDA) under a nitrogen atmosphere.

  8. Selective sorption of oxygen and nitric oxide by an electron-donating flexible porous coordination polymer.

    PubMed

    Shimomura, Satoru; Higuchi, Masakazu; Matsuda, Ryotaro; Yoneda, Ko; Hijikata, Yuh; Kubota, Yoshiki; Mita, Yoshimi; Kim, Jungeun; Takata, Masaki; Kitagawa, Susumu

    2010-08-01

    Porous coordination polymers are materials formed from metal ions that are bridged together by organic linkers and that can combine two seemingly contradictory properties-crystallinity and flexibility. Porous coordination polymers can therefore create highly regular yet dynamic nanoporous domains that are particularly promising for sorption applications. Here, we describe the effective selective sorption of dioxygen and nitric oxide by a structurally and electronically dynamic porous coordination polymer built from zinc centres and tetracyanoquinodimethane (TCNQ) as a linker. In contrast to a variety of other gas molecules (C(2)H(2), Ar, CO(2), N(2) and CO), O(2) and NO are accommodated in its pores. This unprecedented preference arises from the concerted effect of the charge-transfer interaction between TCNQ and these guests, and the switchable gate opening and closing of the pores of the framework. This system provides further insight into the efficient recognition of small gas molecules.

  9. Room temperature synthesis of a Zn(II) metal-organic coordination polymer for dye removal

    NASA Astrophysics Data System (ADS)

    Abbasi, Alireza; Gharib, Maniya; Najafi, Mahnaz; Janczak, Jan

    2016-03-01

    A new one-dimensional (1D) coordination polymer, [Zn(4,4‧-bpy)(H2O)4](ADC)·4H2O (1) (4,4‧-bpy=4,4‧-bipyridine and H2ADC=acetylenedicarboxylic acid), was synthesized at room temperature. The crystal structure of the coordination polymer was determined by single-crystal X-ray diffraction analysis. Compound 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The catalytic activity of 1 was evaluated in the color removal of Bismarck brown as a representative of dye pollutant in water under mild conditions. Coordination polymer 1 exhibited good catalytic activity and stability in the decolorization of Bismarck brown and could be easily recovered and reused for at least three cycles.

  10. Loading of a coordination polymer nanobelt on a functional carbon fiber: a feasible strategy for visible-light-active and highly efficient coordination-polymer-based photocatalysts.

    PubMed

    Xu, Xin-Xin; Yang, Hong-Yu; Li, Zhen-Yu; Liu, Xiao-Xia; Wang, Xiu-Li

    2015-02-23

    To improve the photocatalytic properties of coordination polymers under irradiation in the visible-light region, coordination polymer nanobelts (CPNB) were loaded on functional carbon fiber (FCF) through the use of a simple colloidal blending process. The resulting coordination polymer nanobelt loaded functional carbon fiber composite material (CPNB/FCF) exhibited dramatically improved photocatalytic activity for the degradation of rhodamine B (RhB) under visible-light irradiation. Optical and electrochemical methods illustrated the enhanced photocatalytic activity of CPNB/FCF originated from high separation efficiency of photogenerated electrons and holes on the interface of CPNB and FCF, which was produced by the synergy effect between them. In the composite material, the role of FCF could be described as photosensitizer and good electron transporter. For FCF, the number of functional groups on its surface has a significant influence on the photocatalytic performance of the resulting CPNB/FCF composite material, and an ideal FCF carrier was obtained as a highly efficient CPNB/FCF photocatalyst. CPNB/FCF showed outstanding stability during the degradation of rhodamine B (RhB); thus, the material is suitable for use as a photocatalyst in the treatment of organic dyes in water.

  11. Influence of the supramolecular order on the electrical properties of 1D coordination polymers based materials

    NASA Astrophysics Data System (ADS)

    Musumeci, Chiara; Osella, Silvio; Ferlauto, Laura; Niedzialek, Dorota; Grisanti, Luca; Bonacchi, Sara; Jouaiti, Abdelaziz; Milita, Silvia; Ciesielski, Artur; Beljonne, David; Hosseini, Mir Wais; Samorì, Paolo

    2016-01-01

    The generation, under self-assembly conditions, of coordination polymers on surface based combinations of a terpyridine-antracene-pyridine based tecton and Co(ii) or Pd(ii) cations is primarily governed by the coordination geometry of the metal center (octahedral and square planar respectively). While the octahedral Co(ii) based polymer self-assembles in insulating films exhibiting randomly oriented crystalline domains, the planarity of Pd(ii) based polymers leads to the formation of conductive π-π stacked fibrillar structures exhibiting anisotropically oriented domains. In the latter case, the favorable Pd-Pd and anthracene-anthracene wavefunction overlaps along the fiber direction are responsible for the large electronic couplings between adjacent chains, whereas small electronic couplings are instead found along individual polymer chains. These results provide important guidelines for the design of conductive metal coordination polymers, highlighting the fundamental role of both intra- as well as inter-chain interactions, thus opening up new perspectives towards their application in functional devices.The generation, under self-assembly conditions, of coordination polymers on surface based combinations of a terpyridine-antracene-pyridine based tecton and Co(ii) or Pd(ii) cations is primarily governed by the coordination geometry of the metal center (octahedral and square planar respectively). While the octahedral Co(ii) based polymer self-assembles in insulating films exhibiting randomly oriented crystalline domains, the planarity of Pd(ii) based polymers leads to the formation of conductive π-π stacked fibrillar structures exhibiting anisotropically oriented domains. In the latter case, the favorable Pd-Pd and anthracene-anthracene wavefunction overlaps along the fiber direction are responsible for the large electronic couplings between adjacent chains, whereas small electronic couplings are instead found along individual polymer chains. These results

  12. Ferromagnetic ordering of -[Sm(iii)-radical]n- coordination polymers.

    PubMed

    Fatila, Elisabeth M; Maahs, Adam C; Mills, Michelle B; Rouzières, Mathieu; Soldatov, Dmitriy V; Clérac, Rodolphe; Preuss, Kathryn E

    2016-04-01

    [Sm(hfac)3(boaDTDA)]n is the first coordination compound of a thiazyl-based neutral radical ligand to exhibit ferromagnetic ordering; TC = 3 K. The [Sm(iii)-radical]n species is soluble in common organic solvents and can be sublimed quantitatively. A McConnell I mechanism is implicated in local exchange pathways that contribute to cooperative magnetic properties.

  13. Unprecedented layered coordination polymers of dithiolene group 10 metals: magnetic and electrical properties.

    PubMed

    Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martín, Avelino; Zamora, Félix

    2016-04-21

    One-pot reactions between Ni(ii), Pd(ii) or Pt(ii) salts and 3,6-dichloro-1,2-benzenedithiol (HSC6H2Cl2SH) in KOH medium under argon lead to a series of bis-dithiolene coordination polymers. X-ray analysis shows the presence of a common square planar complex [M(SC6H2Cl2S)2](2-) linked to potassium cations forming either a two-dimensional coordination polymer network for {[K2(μ-H2O)2(μ-thf)(thf)2][M(SC6H2Cl2S)2]}n [M = Ni () and Pd ()] or a one-dimensional coordination polymer for {[K2(μ-H2O)2(thf)6][Pt(SC6H2Cl2S)2]}n (). In the coordination environment of the potassium ions may slightly change leading to the two-dimensional coordination polymer {[K2(μ-H2O)(μ-thf)2][Pt(SC6H2Cl2S)2]}n () that crystallizes together with . The physical characterization of compounds show similar trends, they are diamagnetic and behave as semiconductors. PMID:26974399

  14. Amphiphilic nanocapsules entangled with organometallic coordination polymers for controlled cargo release.

    PubMed

    Liang, Guodong; Ni, Huan; Bao, Suping; Zhu, Fangming; Gao, Haiyang; Wu, Qing; Tang, Ben Zhong

    2014-06-01

    A class of new amphiphilic nanocapsules entangled with organometallic coordination polymers has been developed for the first time. Poly(2-(N,N-dimethyl amino)ethyl methacrylate)-b-polystyrene capped with β-cyclodextrin (β-CD) (CD-PDMAEMA-b-PS) is first synthesized using sequent RAFT polymerization of styrene and 2-(N,N-dimethyl amino)ethyl methacrylate with xanthate modified β-CD as chain transfer agent. The end group of β-CD is allowed to include 4,4'-bipyridine through host-guest inclusion to yield PDMAEMA-b-PS terminated with an inclusion complex of β-CD and bipyridine (bpy-PDMAEMA-b-PS), which is then used as surfactant to prepare emulsion droplets in toluene/water mixture. Upon addition of Ni(II), bipyridine coordinates with Ni(II) to form coordination polymers in the periphery of emulsion droplets, affording amphiphilic capsules entangled with organometallic coordination polymers, as confirmed by GPC, (1)H NMR, SEM, TEM, DLS, and so on. The organometallic coordination polymer capsules are capable of encapsulating organic cargoes. Interestingly, encapsulated cargoes can be extracted from the capsules without damaging the capsules. Such capsules are potential candidates for encapsulating and controlled release of organic cargoes. PMID:24828951

  15. Ferroelectric Coordination Polymers Self-Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands.

    PubMed

    Hui, Joseph K-H; Kishida, Hiroyuki; Ishiba, Keita; Takemasu, Kenta; Morikawa, Masa-Aki; Kimizuka, Nobuo

    2016-09-26

    A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops. The observed ferroelectric properties are explainable by flip-flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive-up-negative-down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics.

  16. Ferroelectric Coordination Polymers Self-Assembled from Mesogenic Zinc(II) Porphyrin and Dipolar Bridging Ligands.

    PubMed

    Hui, Joseph K-H; Kishida, Hiroyuki; Ishiba, Keita; Takemasu, Kenta; Morikawa, Masa-Aki; Kimizuka, Nobuo

    2016-09-26

    A new class of ferroelectric coordination-based polymers has been developed by the self-assembly of lipophilic zinc porphyrin (ZnP) and ditopic bridging ligands. The ligands contain dipolar benzothiadiazole or fluorobenzene units, which are axially coordinated to ZnP with the dipole moments oriented perpendicular to the coordination axes. The coordination-based polymers show ferroelectric characteristics in the liquid crystalline state, as revealed by distinctive hysteresis in the polarization-electric field (P-E) loops and inversion current peaks in current-voltage (I-V) loops. The observed ferroelectric properties are explainable by flip-flop rotation of the dipolar axle ligands induced by the applied electric field, as demonstrated by the positive-up-negative-down (PUND) measurements. The present system provides a new operating principle in supramolecular ferroelectrics. PMID:27527513

  17. Tunable emission in lanthanide coordination polymer gels based on a rationally designed blue emissive gelator.

    PubMed

    Sutar, Papri; Suresh, Venkata M; Maji, Tapas Kumar

    2015-06-18

    Rational design and synthesis of a new low molecular weight gelator (LMWG) having 9,10-diphenylanthracene core and terminal terpyridine is reported. Tb(III) and Eu(III) ion coordination to a LMWG results in green and pink emissive coordination polymer gels, respectively, with coiled nanofiber morphology. Further, control over stoichiometry of LMWG:Tb(III):Eu(III) leads to yellow and white light emitting bimetallic gels. PMID:25995095

  18. Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics

    NASA Astrophysics Data System (ADS)

    Grindy, Scott C.; Learsch, Robert; Mozhdehi, Davoud; Cheng, Jing; Barrett, Devin G.; Guan, Zhibin; Messersmith, Phillip B.; Holten-Andersen, Niels

    2015-12-01

    In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or block copolymer design. Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the relative concentration of two types of metal-ligand crosslinks, we demonstrate control over the material’s mechanical hierarchy of energy-dissipating modes under dynamic mechanical loading, and therefore the ability to engineer a priori the viscoelastic properties of these materials by controlling the types of crosslinks rather than by modifying the polymer itself. This strategy to decouple material mechanics from structure is general and may inform the design of soft materials for use in complex mechanical environments. Three examples that demonstrate this are provided.

  19. Coordination chemistry of 6-thioguanine derivatives with cobalt: toward formation of electrical conductive one-dimensional coordination polymers.

    PubMed

    Amo-Ochoa, Pilar; Alexandre, Simone S; Hribesh, Samira; Galindo, Miguel A; Castillo, Oscar; Gómez-García, Carlos J; Pike, Andrew R; Soler, José M; Houlton, Andrew; Zamora, Félix; Harrington, Ross W; Clegg, William

    2013-05-01

    In this work we have synthetized and characterized by X-ray diffraction five cobalt complexes with 6-thioguanine (6-ThioGH), 6-thioguanosine (6-ThioGuoH), or 2'-deoxy-6-thioguanosine (2'-d-6-ThioGuoH) ligands. In all cases, these ligands coordinate to cobalt via N7 and S6 forming a chelate ring. However, independently of reagents ratio, 6-ThioGH provided monodimensional cobalt(II) coordination polymers, in which the 6-ThioG(-) acts as bridging ligand. However, for 2'-d-6-ThioGuoH and 6-ThioGuoH, the structure directing effect of the sugar residue gives rise to mononuclear cobalt complexes which form extensive H-bond interactions to generate 3D supramolecular networks. Furthermore, with 2'-d-6-ThioGuoH the cobalt ion remains in the divalent state, whereas with 6-ThioGuoH oxidation occurs and Co(III) is found. The electrical and magnetic properties of the coordination polymers isolated have been studied and the results discussed with the aid of DFT calculations, in the context of molecular wires.

  20. Syntheses, structures and photoelectric properties of a series of Cd(II)/Zn(II) coordination polymers and coordination supramolecules

    NASA Astrophysics Data System (ADS)

    Jin, Jing; Han, Xiao; Meng, Qin; Li, Dan; Chi, Yu-Xian; Niu, Shu-Yun

    2013-01-01

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz)2(H2O)]n (1), [Cd1Cd2(btec)(H2O)6]n (2), [Cd(3,4-pdc) (H2O)]n (3), [Zn(2,5-pdc)(H2O)4]·2H2O (4) and {[Zn(2,5-pdc)(H2O)2]·H2O}n (5) (H2bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H4btec=1,2,4,5-benzenetetracarboxylic acid, H2pdc=pyridine-dicarboxylic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, surface photovoltage spectroscopy, XRD, TG analysis, IR and UV-vis spectra and elemental analysis. Structural analyses show that complexes 1-3 are 1D, 2D and 3D Cd(II) coordination polymers, respectively. Complex 4 is a mononuclear Zn(II) complex. Complex 5 is a 3D Zn(II) coordination polymer. The surface photoelectric properties of complexes were investigated by SPS. The results indicate that all complexes exhibit photoelectric responses in the range of 300-600 nm, which reveals that they all possess certain photoelectric conversion properties. By the comparative analyses, it can be found that the species and coordination micro-environment of central metal ion, the species and property of ligands affect the intensity and scope of photoelectric response.

  1. Influence of the supramolecular order on the electrical properties of 1D coordination polymers based materials.

    PubMed

    Musumeci, Chiara; Osella, Silvio; Ferlauto, Laura; Niedzialek, Dorota; Grisanti, Luca; Bonacchi, Sara; Jouaiti, Abdelaziz; Milita, Silvia; Ciesielski, Artur; Beljonne, David; Hosseini, Mir Wais; Samorì, Paolo

    2016-01-28

    The generation, under self-assembly conditions, of coordination polymers on surface based combinations of a terpyridine-antracene-pyridine based tecton and Co(II) or Pd(II) cations is primarily governed by the coordination geometry of the metal center (octahedral and square planar respectively). While the octahedral Co(II) based polymer self-assembles in insulating films exhibiting randomly oriented crystalline domains, the planarity of Pd(II) based polymers leads to the formation of conductive π-π stacked fibrillar structures exhibiting anisotropically oriented domains. In the latter case, the favorable Pd-Pd and anthracene-anthracene wavefunction overlaps along the fiber direction are responsible for the large electronic couplings between adjacent chains, whereas small electronic couplings are instead found along individual polymer chains. These results provide important guidelines for the design of conductive metal coordination polymers, highlighting the fundamental role of both intra- as well as inter-chain interactions, thus opening up new perspectives towards their application in functional devices. PMID:26754960

  2. Synthesis and characterization of linear cerium(IV) Schiff-base coordination polymers

    SciTech Connect

    Chen, H.; Cronin, J.A.; Archer, R.D. . Dept. of Chemistry)

    1994-04-11

    The first soluble linear Schiff-base rare earth coordination polymer, catena-poly[cerium-(4)-[mu]-N,N[prime],N[double prime],N[prime][double prime]-tetrasalicylidene (3,3[prime]-diaminobenzidinato)-O,N,N[prime],O[prime],O[double prime],N[double prime],N[prime][double prime],O[prime][double prime

  3. A ladder type iron(II) coordination polymer with cooperative spin transition.

    PubMed

    Bauer, Wolfgang; Schlamp, Stephan; Weber, Birgit

    2012-10-21

    Ladder type 1D coordination polymers were synthesised with the aim to improve the spin crossover properties of the iron(II) complexes following the concepts of crystal engineering. A wide hysteresis loop (34 K) was observed if rigid linkers were used. The first X-ray structure for a 1D iron(II) ladder is reported.

  4. A barium based coordination polymer for the activity assay of deoxyribonuclease I.

    PubMed

    Song, Chan; Wang, Guan-Yao; Wang, Ya-Ling; Kong, De-Ming; Wang, Yong-Jian; Li, Yue; Ruan, Wen-Juan

    2014-10-01

    A new coordination polymer which shows an unusual 2D inorganic connectivity was constructed. This compound exhibits distinct fluorescence quenching ability to the dye-labeled single-stranded DNA probes with different lengths, based on which an analytical method was developed for the activity assay of deoxyribonuclease I.

  5. New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide.

    PubMed

    Monreal, Marisa J; Seaman, Lani A; Goff, George S; Michalczyk, Ryszard; Morris, David E; Scott, Brian L; Kiplinger, Jaqueline L

    2016-03-01

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge. PMID:26865502

  6. One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties

    NASA Astrophysics Data System (ADS)

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Şahin, Onur

    2016-11-01

    Two new one dimensional (1D) cyanide complexes, namely [M(4-aepy)2(H2O)2][Pt(CN)4], (4-aepy = 4-(2-aminoethyl)pyridine M = Cu(II) (1) or Zn(II) (2)), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The crystallographic analyses reveal that 1 and 2 are isomorphous and isostructural, and crystallize in the monoclinic system and C2 space group. The Pt(II) ions are coordinated by four cyanide-carbon atoms in the square-planar geometry and the [Pt(CN)4]2- ions act as a counter ion. The M(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4-aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. The crystal structures of 1 and 2 are similar each other and linked via intermolecular hydrogen bonding, Pt⋯π interactions to form 3D supramolecular network. Vibration assignments of all the observed bands are given and the spectral features also supported to the crystal structures of the complexes.

  7. Seawater-Assisted Self-Healing of Catechol Polymers via Hydrogen Bonding and Coordination Interactions.

    PubMed

    Li, Jincai; Ejima, Hirotaka; Yoshie, Naoko

    2016-07-27

    It is highly desirable to prevent crack formation in polymeric materials at an early stage and to extend their lifespan, particularly when repairs to these materials would be difficult for humans. Here, we designed and synthesized catechol-functionalized polymers that can self-heal in seawater through hydrogen bonding and coordination. These bioinspired acrylate polymers are originally viscous materials, but after coordination with environmentally safe, common metal cations in seawater, namely, Ca(2+) and Mg(2+), the mechanical properties of the polymers were greatly enhanced from viscous to tough, hard materials. Reduced swelling in seawater compared with deionized water owing to the higher osmotic pressure resulted in greater toughness (∼5 MPa) and self-healing efficiencies (∼80%). PMID:27377859

  8. Fabrication of a PANI/CPs composite material: a feasible method to enhance the photocatalytic activity of coordination polymers.

    PubMed

    Xu, Xin-Xin; Cui, Zhong-Ping; Qi, Ji; Liu, Xiao-Xia

    2013-03-21

    To improve the photocatalytic activity of a coordination polymer in the visible light region, polyaniline (PANI) was loaded onto its surface through a facile in situ chemical oxidation polymerization process. The resulting PANI loaded coordination polymer composite materials with excellent stability exhibit significantly higher photocatalytic activities than the pure coordination polymer photocatalyst on the degradation of methyl orange (MO) under visible light irradiation. This enhancement can be ascribed to the introduction of PANI on the surface of the coordination polymer, which leads to efficient separation of photogenerated electron-hole pairs as well as a significant expansion of the photoresponse region. Finally, we discussed the influence of acidity on the morphology and photocatalytic activity of the composite material. An optimal condition to obtain the PANI loaded coordination polymer composite material with excellent photocatalytic activity has been obtained.

  9. Synthesis and characterization of nanowire coils of organometallic coordination polymers for controlled cargo release.

    PubMed

    Liang, Guodong; Ni, Huan; Bao, Suping; Zhu, Fangming; Gao, Haiyang; Wu, Qing

    2014-06-12

    Nanowire coils of organometallic coordination polymers have been synthesized for the first time by using the emulsion periphery polymerization technique. An amphiphilic triblock copolymer terminated with inclusion complex of β-cyclodextrin and 4,4'-bipyridine self-assembles into oil-in-water emulsion in a toluene/water mixture. Subsequent coordination of bipyridine with Ni(II) in periphery of emulsions results in the formation of coordination polymer nanowire coils. The nanowire coils are composed of nanowires with diameter of 2 nm. Nanowire coils exhibit enhanced thermal stability in contrast to their parent triblock copolymer. Interestingly, nanowire coils are capable of encapsulating organic cargoes. Encapsulated cargoes can be selectively extracted from nanowire coils without damaging nanowire coils. Nanowire coils are potential candidates for encapsulating and controlled release of organic cargoes. PMID:24842771

  10. Synthesis of conjugated polymers containing gallium atoms and evaluation of conjugation through four-coordinate gallium atoms.

    PubMed

    Matsumoto, Takuya; Onishi, Yoshinobu; Tanaka, Kazuo; Fueno, Hiroyuki; Tanaka, Kazuyoshi; Chujo, Yoshiki

    2014-12-25

    The synthesis and analysis of the electronic states of the main-chain type-organogallium polymers are presented. We synthesized the polymers containing four-coordinate gallium atoms by organometal coupling reactions. The synthesized polymers showed good solubility in common organic solvents and enough stability for measuring a series of properties under ambient conditions. In the UV-vis absorption spectra, the electronic interaction through four-coordinate gallium atoms was suggested from the peak shifts of the polymer compared to the model compounds. Theoretical calculation of these molecules supports the extended electronic interaction through the polymer main-chain involving gallium atoms.

  11. Bio-Inspired Composite Interfaces: Controlling Hydrogel Mechanics via Polymer-Nanoparticle Coordination Bond Dynamics

    NASA Astrophysics Data System (ADS)

    Holten-Andersen, Niels

    2015-03-01

    In soft nanocomposite materials, the effective interaction between polymer molecules and inorganic nanoparticle surfaces plays a critical role in bulk mechanical properties. However, controlling these interfacial interactions remains a challenge. Inspired by the adhesive chemistry in mussel threads, we present a novel approach to control composite mechanics via polymer-particle interfacial dynamics; by incorporating iron oxide nanoparticles (Fe3O4 NPs) into a catechol-modified polymer network the resulting hydrogels are crosslinked via reversible coordination bonds at Fe3O4 NP surfaces thereby providing a dynamic gel network with robust self-healing properties. By studying the thermally activated composite network relaxation processes we have found that the polymer-NP binding energy can be controlled by engineering both the organic and inorganic side of the interface.

  12. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    PubMed

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  13. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    PubMed

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  14. Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence

    SciTech Connect

    Zhang, Yingjie; Bhadbhade, Mohan; Karatchevtseva, Inna; Price, Jason R.; Liu, Hao; Zhang, Zhaoming; Kong, Linggen; Čejka, Jiří; Lu, Kim; Lumpkin, Gregory R.

    2015-03-15

    Three new coordination polymers of uranium(VI) with pyromellitic acid (H{sub 4}btca) have been synthesized and structurally characterized. (ED)[(UO{sub 2})(btca)]·(DMSO)·3H{sub 2}O (1) (ED=ethylenediammonium; DMSO=dimethylsulfoxide) has a lamellar structure with intercalation of ED and DMSO. (NH{sub 4}){sub 2}[(UO{sub 2}){sub 6}O{sub 2}(OH){sub 6}(btca)]·~6H{sub 2}O (2) has a 3D framework built from 7-fold coordinated uranyl trinuclear units and btca ligands with 1D diamond-shaped channels (~8.5 Å×~8.6 Å). [(UO{sub 2}){sub 2}(H{sub 2}O)(btca)]·4H{sub 2}O (3) has a 3D network constructed by two types of 7-fold coordinated uranium polyhedron. The unique μ{sub 5}-coordination mode of btca in 3 enables the formation of 1D olive-shaped large channels (~4.5 Å×~19 Å). Vibrational modes, thermal stabilities and fluorescence properties have been investigated. - Graphical abstract: Table of content: three new uranium(VI) coordination polymers with pyromellitic acid (H{sub 4}btca) have been synthesized via room temperature and hydrothermal synthesis methods, and structurally characterized. Two to three dimensional (3D) frameworks are revealed. All 3D frameworks have unique 1D large channels. Their vibrational modes, thermal stabilities and photoluminescence properties have been investigated. - Highlights: • Three new coordination polymers of U(VI) with pyromellitic acid (H{sub 4}btca). • Structures from a 2D layer to 3D frameworks with unique 1D channels. • Unusual µ{sub 5}-(η{sub 1}:η{sub 2}:η{sub 1}:η{sub 2:}η{sub 1}) coordination mode of btca ligand. • Vibrational modes, thermal stabilities and luminescent properties reported.

  15. Nicotine molecularly imprinted polymer: synergy of coordination and hydrogen bonding.

    PubMed

    Huynh, Tan-Phat; B K C, Chandra; Sosnowska, Marta; Sobczak, Janusz W; Nesterov, Vladimir N; D'Souza, Francis; Kutner, Wlodzimierz

    2015-02-15

    Two new bis(2,2'-bithienyl)methane derivatives, one with the zinc phthalocyanine substituent (ZnPc-S16) and the other with the 2-hydroxyethyl substituent (EtOH-S4), were synthesized to serve as functional monomers for biomimetic recognition of nicotine (Nic) by molecular imprinting. Formation of a pre-polymerization complex of the Nic template with ZnPc-S16 and EtOH-S4 was confirmed by both the high negative Gibbs free energy gain, ΔG = -115.95 kJ/mol, calculated using the density functional theory at the B3LYP/3-21G* level, and the high stability constant, Ks = 4.67 × 10(5) M(-1), determined by UV-vis titration in chloroform. A solution of this complex was used to deposit a Nic-templated molecularly imprinted polymer (MIP-Nic) film on an Au electrode of a quartz crystal resonator of EQCM by potentiodynamic electropolymerization. The imprinting factor was as high as ~9.9. Complexation of the Nic molecules by the MIP cavities was monitored with X-ray photoelectron spectroscopy (XPS), as manifested by a negative shift of the binding energy of the Zn 2p3/2 electron of ZnPc-S16 after Nic templating. For sensing applications, simultaneous chronoamperometry (CA) and piezoelectric microgravimetry (PM) measurements were performed under flow-injection analysis conditions. The limit of detection of the CA and PM chemosensing was as low as 40 and 12 µM, respectively. Among them, the CA chemosensing was more selective to the cotinine and myosmine interferences due to the 1.10 V vs. Ag/AgCl discriminating potential of nicotine electro-oxidation applied. Differences in selectivity to the analyte and interferences were interpreted by modeling complexation of Nic and, separately, each of the interferences with a "frozen" MIP-Nic molecular cavity.

  16. Five 8-hydroxyquinolinate-based coordination polymers with tunable structures and photoluminescent properties for sensing nitroaromatics.

    PubMed

    Zhang, Liyan; Sun, Liying; Li, Xinyuan; Tian, Yulan; Yuan, Guozan

    2015-01-01

    Using two 8-hydroxyquinolinate ligands (L1-MOM and L2-MOM) containing 3-pyridyl or 4-pyridyl groups, five novel coordination polymers, namely, [Zn3(L1)6] (1), [Zn(L1)2]·2MeOH (2), [Zn(L2)2] (3), [Cd(L2)2] (4), and [Cd4(L1)6]·13H2O (5), were synthesized and characterized by a variety of techniques. Single-crystal X-ray structures have revealed that these coordination polymers exhibit a structural diversification due to the different choices of metal salts and the effect of pyridyl nitrogen position. Compounds 1-5 exhibited different fluorescence emissions and lifetimes upon excitation in the solid state. The sensing behavior of these polymers was also investigated upon exposure to vapors of various nitroaromatic molecules (analytes). The results show that all five polymers are capable of sensing these nitroaromatic molecules in the vapor phase through fluorescence quenching. Interestingly, 3 exhibits superior sensitivity to the analytes in comparison with other polymers. 2-Nitrotoluene quenches the emission of 3 by as much as 96%.

  17. Novel 3D bismuth-based coordination polymers: Synthesis, structure, and second harmonic generation properties

    SciTech Connect

    Wibowo, Arief C.; Smith, Mark D.; Yeon, Jeongho; Halasyamani, P. Shiv; Loye, Hans-Conrad zur

    2012-11-15

    Two new 3D bismuth containing coordination polymers are reported along with their single crystal structures and SHG properties. Compound 1: Bi{sub 2}O{sub 2}(pydc) (pydc=pyridine-2, 5-dicarboxylate), crystallizes in the monoclinic, polar space group, P2{sub 1} (a=9.6479(9) A, b=4.2349(4) A, c=11.9615(11) A, {beta}=109.587(1) Degree-Sign ), which contains Bi{sub 2}O{sub 2} chains that are connected into a 3D structure via the pydc ligands. Compound 2: Bi{sub 4}Na{sub 4}(1R3S-cam){sub 8}(EtOH){sub 3.1}(H{sub 2}O){sub 3.4} (1R3S cam=1R3S-camphoric acid) crystallizes in the monoclinic, polar space group, P2{sub 1} (a=19.0855(7) A, b=13.7706(5) A, c=19.2429(7) A, {beta}=90.701(1) Degree-Sign ) and is a true 3D coordination polymer. These are two example of SHG compounds prepared using unsymmetric ligands (compound 1) or chiral ligands (compound 2), together with metals that often exhibit stereochemically-active lone pairs, such as Bi{sup 3+}, a synthetic approach that resulted in polar, non-centrosymmetric, 3D metal-organic coordination polymer. - Graphical Abstract: Structures of two new, polar, 3D Bismuth(III)-based coordination polymers: Bi{sub 2}O{sub 2}(pydc) (compound 1), and Bi{sub 4}Na{sub 4}(1R3S-cam){sub 8}(EtOH){sub 3.1}(H{sub 2}O){sub 3.4} (compound 2). Highlights: Black-Right-Pointing-Pointer New, polar, 3D Bismuth(III)-based coordination polymers. Black-Right-Pointing-Pointer First polar bismuth-based coordination polymers synthesized via a 'hybrid' strategy. Black-Right-Pointing-Pointer Combination of stereochemically-active lone pairs and unsymmetrical or chiral ligands. Black-Right-Pointing-Pointer Synthesis of class C-SHG materials based on Kurtz-Perry categories.

  18. Syntheses, structures and photoelectric properties of a series of Cd(II)/Zn(II) coordination polymers and coordination supramolecules

    SciTech Connect

    Jin Jing; Han Xiao; Meng Qin; Li Dan; Chi Yuxian; Niu Shuyun

    2013-01-15

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz){sub 2}(H{sub 2}O)]{sub n} (1), [Cd1Cd2(btec)(H{sub 2}O){sub 6}]{sub n} (2), [Cd(3,4-pdc) (H{sub 2}O)]{sub n} (3), [Zn(2,5-pdc)(H{sub 2}O){sub 4}]{center_dot}2H{sub 2}O (4) and {l_brace} [Zn(2,5-pdc)(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O{r_brace} {sub n} (5) (H{sub 2}bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H{sub 4}btec=1,2,4,5-benzenetetracarboxylic acid, H{sub 2}pdc=pyridine-dicarboxylic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, surface photovoltage spectroscopy, XRD, TG analysis, IR and UV-vis spectra and elemental analysis. Structural analyses show that complexes 1-3 are 1D, 2D and 3D Cd(II) coordination polymers, respectively. Complex 4 is a mononuclear Zn(II) complex. Complex 5 is a 3D Zn(II) coordination polymer. The surface photoelectric properties of complexes were investigated by SPS. The results indicate that all complexes exhibit photoelectric responses in the range of 300-600 nm, which reveals that they all possess certain photoelectric conversion properties. By the comparative analyses, it can be found that the species and coordination micro-environment of central metal ion, the species and property of ligands affect the intensity and scope of photoelectric response. - Graphical abstract: Five Cd(II)/Zn(II) complexes have been hydrothermally synthesized and characterized. The photoelectric properties were studied with SPS. The species and coordination micro-environment of central metal ion, the species and property of ligands all affect the photoelectric responses. Highlights: Black-Right-Pointing-Pointer Five Cd/Zn complexes have been synthesized and characterized. Black-Right-Pointing-Pointer The SPS results indicate they possess obvious photoelectric conversion property. Black-Right-Pointing-Pointer The species and coordination environment of central metal ion affect SPS. Black-Right-Pointing-Pointer The species and property of ligands affect SPS

  19. Soluble 1D coordination polymers based on dendron-functionalized bispyridine ligand for linking between immobilized molecules on substrates.

    PubMed

    Tokuhisa, Hideo; Kanesato, Masatoshi

    2005-10-11

    As a monomeric ligand for a soluble 1D coordination polymer, a benzyl-ether based dendrimer having a rigid 4,4'-bispyridine ligand at the focal point has been synthesized and the coordination chemistry with Pd(II) investigated by nuclear magnetic resonance, ultraviolet-visible and fluorescence spectroscopies, gel permeation chromatography measurement, and X-ray photoelectron spectroscopy. As a result, it was found that the synthesized dendrimer forms a stable, soluble Pd(II) coordination polymer with rough estimation of degree of polymerization of 10 in organic solvents. Furthermore, through the coordination polymer we attempted to link fourth-generation poly(amidoamine) dendrimers (PAMAM) individually immobilized on mica and confirmed the interconnection of the PAMAM through coordination polymers by atomic force microscopy.

  20. Application of a silver-olefin coordination polymer as a catalytic curing agent for self-healing epoxy polymers

    NASA Astrophysics Data System (ADS)

    Everitt, D. T.; Coope, T. S.; Trask, R. S.; Wass, D. F.; Bond, I. P.

    2015-05-01

    A silver-olefin based coordination polymer was prepared in a simple, one step process to act as an initiator to facilitate the ring-opening polymerization of epoxides. Thermal analysis found the complex to be capable of curing a range of commercially available epoxy resins used in the manufacture of conventional composite materials. Curing of the oligomeric diglycidyl ether bisphenol A resin, Epon 828, in combination with a non-toxic solvent, ethyl phenylacetate, was studied by differential scanning calorimetry. The mechanical characterization of the resultant cured polymers was conducted by single lap shear tests. Tapered double cantilever beam (TDCB) test specimens containing 2.5 pph of silver-olefin initiator, both with and without embedded microcapsules, were analyzed for their healing performance. Healing efficiency values were found to be strongly dependent on the applied healing temperature. A mean recovery of 74% fracture load was found in TDCB samples after being healed at 70 °C for 48 h.

  1. Metal Coordination Stoichiometry Controlled Formation of Linear and Hyperbranched Supramolecular Polymers.

    PubMed

    Lin, Cuiling; Xu, Luonan; Huang, Libo; Chen, Jia; Liu, Yuanyuan; Ma, Yifan; Ye, Feixiang; Qiu, Huayu; He, Tian; Yin, Shouchun

    2016-09-01

    Controlling the topologies of polymers is a hot topic in polymer chemistry because the physical and/or chemical properties of polymers are determined (at least partially) by their topologies. This study exploits the host-guest interactions between dibenzo-24-crown-8 and secondary ammonium salts and metal coordination interactions between 2,6-bis(benzimidazolyl)-pyridine units with metal ions (Zn(II) and/or Eu(III) ) as orthogonal non-covalent interactions to prepare supramolecular polymers. By changing the ratios of the metal ion additives (Zn(NO3 )2 and Eu(NO3 )3 ) linkers to join the host-guest dimeric complex, the linear supramolecular polymers (100 mol% Zn(NO3 )2 per ligand) and hyperbranched supramolecular polymers (97 mol% Zn(NO3 )2 and 3 mol% Eu(NO3 )3 per ligand) are separately and successfully constructed. This approach not only expands topological control over polymeric systems, but also paves the way for the functionalization of smart and adaptive materials. PMID:27377646

  2. Synthesis, structure, luminescence and photocatalytic properties of an uranyl-2,5-pyridinedicarboxylate coordination polymer

    NASA Astrophysics Data System (ADS)

    Si, Zhen-Xiu; Xu, Wei; Zheng, Yue-Qing

    2016-07-01

    An uranium coordination polymer, namely [(UO2(pydc)(H2O)]·H2O (1) (H2pydc=2,5-pyridinedicarboxylic acid), has been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 1D chain coordination polymer, in which UO22+ ions are bridged by 2,5-pyridinedicarboxylate ligands and the chains are connected into a 3D supramolecular network by O-H···O hydrogen bond interactions and π-π stacking interactions. The photocatalytic properties of 1 for degradation of methylene blue (MB), Rhodamine B (RhB) and methyl orange (MO) under Hg-lamp irradiation have been performed, and the amount of the catalyst as well as Hg-lamp irradiation with different power on the photodegradation efficiency of MB have been investigated. Elemental analyses, infrared spectroscopy, TG-DTA analyses and luminescence properties were also discussed.

  3. Single-crystal X-ray diffraction studies on structural transformations of porous coordination polymers.

    PubMed

    Zhang, Jie-Peng; Liao, Pei-Qin; Zhou, Hao-Long; Lin, Rui-Biao; Chen, Xiao-Ming

    2014-08-21

    X-Ray single-crystal diffraction has been the most straightforward and important technique in structural determination of crystalline materials for understanding their structure-property relationships. This powerful tool can be used to directly visualize the precise and detailed structural information of porous coordination polymers or metal-organic frameworks at different states, which are unique for their flexible host frameworks compared with conventional adsorbents. With a series of selected recent examples, this review gives a brief overview of single-crystal X-ray diffraction studies and single-crystal to single-crystal transformations of porous coordination polymers under various chemical and physical stimuli such as solvent and gas sorption/desorption/exchange, chemical reaction and temperature change.

  4. Two Zn coordination polymers with meso-helical chains based on mononuclear or dinuclear cluster units

    NASA Astrophysics Data System (ADS)

    Qin, Ling; Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang

    2016-07-01

    Two zinc coordination polymers {[Zn2(TPPBDA)(oba)2]·DMF·1.5H2O}n (1), {[Zn(TPPBDA)1/2(tpdc)]·DMF}n (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn2(CO2)4] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn2+. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymers have been investigated in detail.

  5. A Perylene-Based Microporous Coordination Polymer Interacts Selectively with Electron-Poor Aromatics.

    PubMed

    Tran, Ly D; Ma, Jialiu; Wong-Foy, Antek G; Matzger, Adam J

    2016-04-11

    The design, synthesis, and properties of the new microporous coordination polymer UMCM-310 are described. The unique electronic character of the perylene-based linker enables selective interaction with electron-poor aromatics leading to efficient separation of nitroaromatics. UMCM-310 possesses high surface area and large pore size and thus permits the separation of large organic molecules based on adsorption rather than size exclusion.

  6. Picogram sensing of trinitrophenol in aqueous medium through a water stable nanoscale coordination polymer.

    PubMed

    Asha, K S; Vaisakhan, G S; Mandal, Sukhendu

    2016-06-01

    A water stable nanoscale coordination polymer (CP) can detect trinitrophenol (TNP) in an aqueous medium at a record-picogram level (∼1.66 pg cm(-2)) with a detection limit of 1.66 ppb. This is a simple and low-cost method for the detection of TNP in aqueous media in contact mode, taking advantage of the unique structural arrangement of the as-synthesized CP and the associated photophysical properties.

  7. Terbium-based coordination polymer nanoparticles for detection of ciprofloxacin in tablets and biological fluids.

    PubMed

    Tan, Hongliang; Zhang, Li; Ma, Chanjiao; Song, Yonghai; Xu, Fugang; Chen, Shouhui; Wang, Li

    2013-11-27

    The metal-organic coordination polymers with tunable structures and properties have been rapidly emerging as very important functional materials. In this work, we prepared terbium (Tb(3+))-based coordination polymer nanoparticles (CPNPs) by employing adenine (Ad) as bridging ligands. The CPNPs was further used as a receptor reagent for ciprofloxacin (CF) detection in aqueous solution. Addition of CF induces a typical emission of Tb(3+) due to the formation of Ad/Tb-CF complex and the sensitization of CF. The fluorescent intensity of Tb(3+) was enhanced linearly with increasing the CF concentration from 60 nM to 14 μM. The detection limit for CF in aqueous solution is 60 nM. The Ad/Tb CPNPs was successfully applied to detect CF in tablet and urine samples and showed a satisfactory result. Compared with other methods, the proposed method is advantageous because that it provides a very simple strategy for CF detection, which does not require complicated sample pretreatment processes or special reaction media. The proposed strategy could be contributed to expand the potential applications of lanthanide coordination polymers in biological and environmental fields.

  8. In situ composition and luminescence of terbium coordination polymers/PEMA hybrid thick films

    NASA Astrophysics Data System (ADS)

    Yan, Bing; Wang, Qian-Ming

    2004-12-01

    Some terbium coordination polymers with infinite chain polymeric structures were in situ composed with ethyl methacrylate (EMA). With the polymerization of EMA monomer and the formation of terbium coordination polymers of methylbenzoic acid and 2-chloro benzoic acid, the transparent hybrid thick films composed by [Tb(OMBA)3]n ([Tb(MMBA)3]n, [Tb(OCBA)3]n) and poly ethyl methacrylate (PEMA) have been achieved. The luminescence properties and energy transfer for these polymeric composite films were studied with absorption spectra, fluorescent excitation and emission spectra in detail. All the hybrid thick films composed with terbium coordination polymers show the characteristic strong green emission of terbium ions, which implies the same energy transfer mechanism as the pure complex and the hybrid composite film is a suitable substrate for the luminescence of terbium ions. In the range of composing concentration of luminescent species (0.005, 0.01, 0.025, 0.05, 0.1 and 0.2 mmol/7.5 ml EMA), emission intensities increases with the increasing of corresponding composing concentration and concentration quenching effect has not taken place.

  9. Synthesis, structure and fluorescence properties of a novel 3D Sr(II) coordination polymer

    NASA Astrophysics Data System (ADS)

    Tan, Yu-Hui; Xu, Qing; Gu, Zhi-Feng; Gao, Ji-Xing; Wang, Bin; Liu, Yi; Yang, Chang-Shan; Tang, Yun-Zhi

    2016-09-01

    Solvothermal reaction of 2,2‧-bipyridine-5,5‧-dicarboxylic acid (H2bpdc) and SrCl2 affords a novel coordination polymer [Sr(Hbpdc)2]n1. X-ray structure determination shows that 1 exhibits a novel three-dimensional network. The unique Sr II cation sits on a two-fold axis and coordinated by four O-atom donors from four Hbptc- ligands and four N-atom donors from two Hbptc- ligands in distorted dodecahedral geometry. In 1 each Sr II cation connects to six different Hbptc- ligands and each Hbptc- ligand bridges three different Sr II cations which results in the formation of a three-dimensional polymeric structure. Corresponding to the free ligand, the fluorescent emission of complex 1 display remarkable "Einstain" shifts, which may be attributed to the coordination interaction of Sr atoms, thus reduce the rigidity of pyridyl rings.

  10. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    SciTech Connect

    Peresypkina, Eugenia V.; Samsonenko, Denis G.; Vostrikova, Kira E.

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  11. A responsive supramolecular polymer formed by orthogonal metal-coordination and cryptand-based host-guest interaction.

    PubMed

    Wei, Peifa; Xia, Binyuan; Zhang, Yanyan; Yu, Yihua; Yan, Xuzhou

    2014-04-18

    Herein, a cation responsive linear supramolecular polymer was constructed in an orthogonal fashion by unifying the themes of coordination-driven self-assembly and cryptand-based host-guest interaction. PMID:24609282

  12. Micromolding of a Highly Fluorescent Reticular Coordination Polymer: Solvent-Mediated Reconfigurable Polymerization in a Soft Lithographic Mold

    SciTech Connect

    Y You; H Yang; J Chung; J Kim; Y Jung; S Park

    2011-12-31

    Coordination polymerization of pyridine-based ligands and zinc or silver ions was controlled by soft lithographic micromolding in capillaries. The polymer patterns that are produced are highly fluorescent and supramolecularly structured.

  13. Syntheses, structural analyses and luminescent property of four alkaline-earth coordination polymers

    SciTech Connect

    Zhang, Sheng; Qu, Xiao-Ni; Xie, Gang; Wei, Qing; Chen, San-Ping

    2014-02-15

    Four alkaline-earth coordination polymers, [Ba(Pzdc)(H{sub 2}O)]{sub n} (1), [Ba(Pzdc)]{sub n} (2), [AgSr(Pzdc)(NO{sub 3})(H{sub 2}O)]{sub n} (3), [Ag{sub 2}Ca(Pzdc){sub 2}(H{sub 2}O)]{sub n} (4) (H{sub 2}Pzdc=2, 3-pyrazinedicarboxylic acid) have been synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 afford 2D layer networks generated by one-dimensional chains containing the [Ba{sub 2}O{sub 11}N] units. Compound 3 is of 2D mixed-metal coordination network formed by one-dimensional chain units, while 4 is of a 3D heterometallic framework. Interestingly, 1 and 2 can undergo reversible SCSC structural transformation upon dehydration/rehydration of coordinated water molecules. In addition, the π–π stacking interactions dominate fluorescent properties of compounds 1 and 2. - Graphical abstract: Four new coordination polymers [Ba(Pzdc)(H{sub 2}O)]{sub n} (1), [Ba(Pzdc)]{sub n} (2), [AgSr(Pzdc)(NO{sub 3})(H{sub 2}O)]{sub n} (3), [Ag{sub 2}Ca(Pzdc){sub 2}(H{sub 2}O)]{sub n} (4) (H{sub 2}Pzdc=2, 3-pyrazinedicarboxylic acid) have been synthesized. Compounds 1–3 display 2D topology structures and compound 4 exhibits a 3D topology structure. Fortunately, 1 and 2 undergo reversible dehydration/rehydration of coordinated water molecules. Display Omitted - Highlights: • All structures are generated by 1D chains. • 1 and 2 show reversible dehydration/rehydration of coordinated water molecules. • The π–π stacking interactions dominate fluorescent properties of compounds 1 and 2.

  14. Hierarchical effect behind the supramolecular chirality of silver(I)-cysteine coordination polymers.

    PubMed

    Randazzo, Rosalba; Di Mauro, Alessandro; D'Urso, Alessandro; Messina, Gabriele C; Compagnini, Giuseppe; Villari, Valentina; Micali, Norberto; Purrello, Roberto; Fragalà, Maria Elena

    2015-04-01

    Cysteine is a sulfur-containing amino acid that easily coordinates to soft metal ions and grafts to noble metal surfaces. Recently, chiroptical activity of Ag(+)/cysteine coordination polymers has been widely studied, while, on the other hand, the appearance of a plasmon-enhanced circular dichroic signal (PECD) at the plasmonic spectral region (λ > 400 nm) has been observed for AgNPs capped with chiral sulfur-containing amino acids. These two events are both potentially exploited for sensing applications. However, the presence of Ag(+) ions in AgNP colloidal solution deals with the competition of cysteine grafting at the metal NP surface and/or metal ion coordination. Herein we demonstrate that the chiroptical activity observed by adding cysteine to AgNP colloids prepared by pulsed laser ablation in liquids (PLAL) is mainly related to the formation of CD-active Ag(+)/cysteine supramolecular polymers. The strict correlation between supramolecular chirality and hierarchical effects, driven by different chemical environments experienced by cysteine when different titration modalities are used, is pivotal to validate cysteine as a fast and reliable probe to characterize the surface oxidation of AgNPs prepared by pulsed laser ablation in liquids by varying the laser wavelengths.

  15. Coordination polymers assembled from semirigid fluorene-based ligand: A couple of enantiomers

    NASA Astrophysics Data System (ADS)

    Li, Liang; Wang, Zihao; Chen, Qiang; Zhou, Xinhui; yang, Tao; Zhao, Qiang; Huang, Wei

    2015-11-01

    A couple of Mg(II)-based coordination polymer enantiomers [MgL(DMF)(H2O)3]n (R-MgL and S-MgL), and a Zn(II)-based coordination polymer [ZnL(DMF)]n (ZnL) have been synthesized by the solvothermal reactions between the achiral ligand 4,4‧-(9,9-dimethyl-9H-fluorene-2,7-diyl)dibenzoic acid (H2L) and the corresponding metal salts. The MgL was obtained as the racemic conglomerate from the one pot reaction. The single crystal X-ray structural analyses reveal that MgL crystallize in the chiral space group P21 and possesses the right- or left-handed homochiral 1D Mg-O-C helical chain. The ZnL crystallize in the non-centrosymmetrical space group Aba2 and possesses the 2D network comprised of 1D Zn-O-C meso-helical chains and ligands. The MgL and ZnL complexes exhibit strong coordination-perturbed ligand-centered blue emissions when excited at 320 nm. Their second-order nonlinear optical effects and thermal properties have also been studied.

  16. Picogram sensing of trinitrophenol in aqueous medium through a water stable nanoscale coordination polymer

    NASA Astrophysics Data System (ADS)

    Asha, K. S.; Vaisakhan, G. S.; Mandal, Sukhendu

    2016-06-01

    A water stable nanoscale coordination polymer (CP) can detect trinitrophenol (TNP) in an aqueous medium at a record-picogram level (~1.66 pg cm-2) with a detection limit of 1.66 ppb. This is a simple and low-cost method for the detection of TNP in aqueous media in contact mode, taking advantage of the unique structural arrangement of the as-synthesized CP and the associated photophysical properties.A water stable nanoscale coordination polymer (CP) can detect trinitrophenol (TNP) in an aqueous medium at a record-picogram level (~1.66 pg cm-2) with a detection limit of 1.66 ppb. This is a simple and low-cost method for the detection of TNP in aqueous media in contact mode, taking advantage of the unique structural arrangement of the as-synthesized CP and the associated photophysical properties. Electronic supplementary information (ESI) available: Experimental section, a scheme for nano CP synthesis, a table for crystallographic data and selected bond lengths, figures of coordination modes of metal and ligand, IR, TGA, DLS and PXRD characterization of the micro/nano sample, SEM and TEM images, N2 adsorption-desorption plot, the optical properties of 1 in DMF and photophysical studies and NMR studies of the compound. See DOI: 10.1039/c5nr08159a

  17. Hierarchical effect behind the supramolecular chirality of silver(I)-cysteine coordination polymers.

    PubMed

    Randazzo, Rosalba; Di Mauro, Alessandro; D'Urso, Alessandro; Messina, Gabriele C; Compagnini, Giuseppe; Villari, Valentina; Micali, Norberto; Purrello, Roberto; Fragalà, Maria Elena

    2015-04-01

    Cysteine is a sulfur-containing amino acid that easily coordinates to soft metal ions and grafts to noble metal surfaces. Recently, chiroptical activity of Ag(+)/cysteine coordination polymers has been widely studied, while, on the other hand, the appearance of a plasmon-enhanced circular dichroic signal (PECD) at the plasmonic spectral region (λ > 400 nm) has been observed for AgNPs capped with chiral sulfur-containing amino acids. These two events are both potentially exploited for sensing applications. However, the presence of Ag(+) ions in AgNP colloidal solution deals with the competition of cysteine grafting at the metal NP surface and/or metal ion coordination. Herein we demonstrate that the chiroptical activity observed by adding cysteine to AgNP colloids prepared by pulsed laser ablation in liquids (PLAL) is mainly related to the formation of CD-active Ag(+)/cysteine supramolecular polymers. The strict correlation between supramolecular chirality and hierarchical effects, driven by different chemical environments experienced by cysteine when different titration modalities are used, is pivotal to validate cysteine as a fast and reliable probe to characterize the surface oxidation of AgNPs prepared by pulsed laser ablation in liquids by varying the laser wavelengths. PMID:25781213

  18. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

    SciTech Connect

    Jin, Jun-Cheng; Tong, Wen-Quan; Fu, Ai-Yun; Xie, Cheng-Gen; Chang, Wen-Gui; Wu, Ju; Xu, Guang-Nian; Zhang, Ya-Nan; Li, Jun; Li, Yong; Yang, Peng-Qi

    2015-05-15

    Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2{sub 1} helical chains. While the Nd(III) ions are bridged through μ{sub 2}-HIDC{sup 2−} and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2{sub 1} helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2{sub 1} helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature.

  19. Understanding the Structure of Reversible Coordination Polymers Based on Europium in Electrostatic Assemblies Using Time-Resolved Luminescence.

    PubMed

    Xu, Limin; Xie, Mengqi; Huang, Jianbin; Yan, Yun

    2016-06-14

    In situ characterization of the structure of reversible coordination polymers remains a challenge because of their dynamic and concentration-responsive nature. It is especially difficult to determine these structures in their self-assemblies where their degree of polymerization responds to the local concentration. In this paper, we report on the structure of reversible lanthanide coordination polymers in electrostatic assemblies using time-resolved luminescence (TRL) measurement. The reversible coordinating system is composed of the bifunctional ligand 1,11-bis(2,6-dicarboxypyridin-4-yloxy)-3,6,9-trioxaundecane (L2EO4) and europium ion Eu(3+). Upon mixing with the positively charged diblock copolymer poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP41-b-PEO205), electrostatic polyion micelles are formed and the negatively charged L2EO4-Eu coordination complex simultaneously transforms into coordination "polymers" in the micellar core. By virtue of the water-sensitive luminescence of Eu(3+), we are able to obtain the structural information of the L2EO4-Eu coordination polymers before and after the formation of polyion micelles. Upon analyzing the fluorescence decay curves of Eu(3+) before and after micellization, the fraction of Eu(3+) fully coordinated with L2EO4 is found to increase from 32 to 83%, which verifies the occurrence of chain extension of the L2EO4-Eu coordination polymers in the micellar core. Our work provides a qualitative picture for the structure change of reversible coordination polymers, which allows us to look into these "invisible" structures.

  20. Understanding the Structure of Reversible Coordination Polymers Based on Europium in Electrostatic Assemblies Using Time-Resolved Luminescence.

    PubMed

    Xu, Limin; Xie, Mengqi; Huang, Jianbin; Yan, Yun

    2016-06-14

    In situ characterization of the structure of reversible coordination polymers remains a challenge because of their dynamic and concentration-responsive nature. It is especially difficult to determine these structures in their self-assemblies where their degree of polymerization responds to the local concentration. In this paper, we report on the structure of reversible lanthanide coordination polymers in electrostatic assemblies using time-resolved luminescence (TRL) measurement. The reversible coordinating system is composed of the bifunctional ligand 1,11-bis(2,6-dicarboxypyridin-4-yloxy)-3,6,9-trioxaundecane (L2EO4) and europium ion Eu(3+). Upon mixing with the positively charged diblock copolymer poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP41-b-PEO205), electrostatic polyion micelles are formed and the negatively charged L2EO4-Eu coordination complex simultaneously transforms into coordination "polymers" in the micellar core. By virtue of the water-sensitive luminescence of Eu(3+), we are able to obtain the structural information of the L2EO4-Eu coordination polymers before and after the formation of polyion micelles. Upon analyzing the fluorescence decay curves of Eu(3+) before and after micellization, the fraction of Eu(3+) fully coordinated with L2EO4 is found to increase from 32 to 83%, which verifies the occurrence of chain extension of the L2EO4-Eu coordination polymers in the micellar core. Our work provides a qualitative picture for the structure change of reversible coordination polymers, which allows us to look into these "invisible" structures. PMID:27228142

  1. Coordination polymers built from 1,4-bis(imidazol-1-ylmethyl)benzene: from crystalline to amorphous.

    PubMed

    Adarsh, N N; Novio, Fernando; Ruiz-Molina, Daniel

    2016-07-28

    The supramolecular chemistry of the bis-imidazole ligand 1,4-bis(imidazol-1-ylmethyl)benzene, popularly known as bix, has been explored by various researchers in order to synthesize functional coordination polymers (CPs). The flexibility of the bix ligand, its unpredictable conformation and its coordination behaviour with transition metal ions have resulted in a huge number of structurally diverse and functionally intriguing CPs. In this perspective review we discuss the progress in CPs of bix between 1997 and today. More precisely, this review emphasizes the developments in functional supramolecular coordination polymers built from the bix ligand, from crystalline materials to amorphous nanomaterials. PMID:27335273

  2. Structural Diversity of Cadmium(II) Coordination Polymers Induced by Tuning the Coordination Sites of Isomeric Ligands.

    PubMed

    Liu, Bo; Zhou, Hui-Fang; Hou, Lei; Wang, Jian-Ping; Wang, Yao-Yu; Zhu, Zhonghua

    2016-09-01

    When the coordination sites of ligands were shifted, the solvothermal reactions of four positional isomeric asymmetrical pyridyldicarboxylatic acids with Cd(NO3)2 generated four new coordination polymers, [Cd(L1)(DMF)3]·DMF·H2O (1), [H2N(CH3)2]2[Cd(L2)2]·3DMF·H2O (2), [Cd(L3)(H2O)2] (3), and [Cd(L4)]·1.5DMF (4), where DMF = N,N-dimethylformamide, H2L1 = 2-(3'-carboxylphenyl)isonicotinic acid, H2L2 = 2-(4'-carboxylphenyl)isonicotinic acid, H2L3 = 5-(3'-carboxylphenyl)nicotic acid, and H2L4 = 2-(3'-pyridyl)terephthalic acid. 1 shows a rare 2D fabric structure. 2 discloses a grid-layer structure with heterochiral helical chains and in which three sets of layers stack in different directions, affording an unprecedented 2D + 2D + 2D → 3D polycatenating framework with 3D intersecting porous systems. 3 also displays a 2D layer possessing strong intralayer π···π interactions and interlayer hydrogen bonds. 4 contains a rare Cd2(COO)4 paddle-wheel unit and forms a 3D framework with 1D open channels. The carboxyl and pyridyl groups of the positional isomeric H2L1-H2L4 ligands show distinct bridging fashions, which leads to the production of versatile architectures of 1-4, and their effects on the crystal structures are discussed. 1-4 reveal solid-state photoluminescence stemming from intraligand charge transfer. 2 and 4 show high selectivity for CO2 over CH4 but with different CO2 adsorption enthalpies. Grand canonical Monte Carlo simulations identified the multiple adsorption sites in 2 for CO2. PMID:27513092

  3. Syntheses, crystal structures, and properties of new metal-5-bromonicotinate coordination polymers

    SciTech Connect

    Li, Wenjie; Li, Guoting; Lv, Lulu; Zhao, Hong; Wu, Benlai

    2015-05-15

    Four metal–5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (1), [Ni(Brnic){sub 2}]{sub n} (2), [Ni(Brnic)(bpy)(H{sub 2}O){sub 2}]{sub n}·n(Brnic)·4.5nH{sub 2}O (3), and [Co{sub 2}(Brnic){sub 3}(bpy){sub 2}(OH)]{sub n}·nH{sub 2}O (4) have been synthesized and structurally characterized (bpy=4,4′-bipyridine). Complex 1 has corrugated (4,4) sheets formed by μ-Brnic ligands and planar nodes Fe(II). As for 2–4, they all built up from Brnic-bridged dinuclear subunits, but have very different structure features. Complex 2 is a twin-like polymer with (4,4) layers formed by twin paddle-wheel [Ni{sub 2}(Brnic){sub 4}] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni{sub 2}(Brnic){sub 2}] and trigons [Co{sub 2}(Brnic){sub 3}(OH)], 6{sup 3}-topological cationic layers with nanosized grids of 3 and chiral ladder-type double chains of 4 formed, respectively. Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules 1–4. The thermostabilities of all compounds have been discussed in detail. Moreover, the magnetic investigations of 2 and 4 indicate that there exist antiferromagnetic interactions in the paddle-wheel [Ni{sub 2}(Brnic){sub 4}] and trigon [Co{sub 2}(Brnic){sub 3}(OH)] cores, respectively. - Highlights: • Four novel metal–5-bromonicotinate coordination polymers have been synthesized. • Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules. • Antiferromagnetic interactions in nickel(II) paddle-wheel and cobalt(II) trigon cores were observed.

  4. Synthesis and characterization of 1D iron(II) spin crossover coordination polymers with hysteresis.

    PubMed

    Bauer, Wolfgang; Lochenie, Charles; Weber, Birgit

    2014-02-01

    Purposeful ligand design was used for the synthesis of eight new 1D iron(II) spin crossover coordination polymers aiming for cooperative spin transitions with hysteresis. The results from magnetic measurements and X-ray structure analysis show that the combination of rigid linkers and a hydrogen bond network between the 1D chains is a promising tool to reach this goal. Five of the eight new samples show a cooperative spin transition with hysteresis with up to 43 K wide hysteresis loops.

  5. Magnetic nanosized {M(II)24}-wheel-based (M = Co, Ni) coordination polymers.

    PubMed

    Li, Jia; Tao, Jun; Huang, Rong-Bin; Zheng, Lan-Sun

    2012-06-01

    Two 3D coordination polymers, [Co(24)(OH)(12)(SO(4))(12)(ip)(6)(DMSO)(18)(H(2)O)(6)]·(DMSO)(6)(EtOH)(6)(H(2)O)(36) (1·guests, ip = isophthalate) and [Ni(24)(OH)(12)(SO(4))(12)(ip)(6)(DMSO)(12)(H(2)O)(12)]·(DMSO)(6)(EtOH)(6)(H(2)O)(20) (2·guests), constructed with nanosized tetraicosanuclear Co(II) and Ni(II) wheels are solvothermally synthesized. Both complexes show intra- and interwheel dominant antiferromagnetic interactions.

  6. Selective Adsorption of CO2 from Light Gas Mixtures Using a Structurally Dynamic Porous Coordination Polymer**

    SciTech Connect

    Kristi L. Kauffman, Jeffrey T. Culp, Andrew J. Allen, Laura Espinal, Winnie Wong-Ng, Thomas D. Brown, Angela Goodman, Mark P. Bernardo, Russel J. Pancoast, Danielle Chirdon, Christopher Matranga*

    2010-01-01

    The selective adsorption of CO{sub 2} from mixtures with N{sub 2}, CH{sub 4}, and N{sub 2}O in a dynamic porous coordination polymer (see monomer structure) was evaluated by ATR-FTIR spectroscopy, GC, and SANS. All three techniques indicate highly selective adsorption of CO{sub 2} from CO{sub 2}/CH{sub 4} and CO{sub 2}/N{sub 2} mixtures at 30 C, with no selectivity observed for the CO{sub 2}/N{sub 2}O system.

  7. A novel 2D porous indium coordination polymer with tunable luminescent property

    NASA Astrophysics Data System (ADS)

    Li, Xuejiao; Wang, Fangfang; Yang, He; Xu, Bo; Li, Cuncheng

    2016-08-01

    A new Indium coordination polymer [In(pda)1.5(phen)]n1 based on 1,4-phenylenediacetic acid (H2pda) and phen = 1,10-phenanthroline was obtained under hydrothermal condition and further characterized by single crystal X-ray analysis and other physicochemical studies such as infrared spectrum (IR), elemental analysis, thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Structure analysis reveals that complex 1 exhibits 2D porous (6,3) connected layer structure. Luminescent property of 1 was investigated both in the solid state and in different solvents and the results indicated that complex 1 demonstrates distinct solvent dependent luminescent property.

  8. Lattice architecture effect on the cooperativity of spin transition coordination polymers

    SciTech Connect

    Chiruta, Daniel; Jureschi, Catalin-Maricel; Rotaru, Aurelian E-mail: rotaru@eed.usv.ro; Linares, Jorge E-mail: rotaru@eed.usv.ro; Garcia, Yann

    2014-02-07

    We have investigated in the framework of the Ising-like model, by means of Monte Carlo Metropolis method with open boundary condition, the architecture effect on the cooperativity of spin transition coordination polymers. We have analyzed the influence of several physical parameters (size, pressure, and edge effects) on different lattice architectures which were in good agreement with reported experimental data. We show that the cooperativity of a spin crossover system, characterized by the same number of molecules and the same short- and long-range interaction parameters, is progressively enhanced when going from a 1D chain to a 1D ladder type lattice and to a 2D square lattice.

  9. Efficient fixation of CO2 by a zinc-coordinated conjugated microporous polymer.

    PubMed

    Xie, Yong; Wang, Ting-Ting; Yang, Rui-Xia; Huang, Nian-Yu; Zou, Kun; Deng, Wei-Qiao

    2014-08-01

    Zinc-coordinated conjugated microporous polymers (Zn-CMPs), prepared by linking salen zinc and 1,3,5-triethynylbenzene, exhibit extraordinary activities (turnover frequencies of up to 11600 h(-1) ), broad substrate scope, and group tolerance for the synthesis of functional organic carbonates by coupling epoxides with CO2 at 120 °C and 3.0 MPa without the use of additional solvents. The catalytic activity of Zn-CMP is comparable to those of homogeneous catalysts and superior to those of other heterogeneous catalysts. This catalyst could be reused more than ten times without a significant decrease in performance.

  10. Coronates, spherical containers, bowl-shaped surfaces, porous 1D-, 2D-, 3D-metallo-coordination polymers, and metallodendrimers.

    PubMed

    Saalfrank, Rolf W; Scheurer, Andreas

    2012-01-01

    Supramolecular coordination cages and polymers bear exceptional advantages over their organic counterparts. They are available in one-pot reactions and in high yields and display physical properties that are generally inaccessible with organic species. Moreover, their weak, reversible, noncovalent bonding interactions facilitate error checking and self-correction. This review emphasizes the achievements in supramolecular coordination container as well as polymer chemistry initiated by serendipity and their materialization based on rational design. The recognition of similarities in the synthesis of different supramolecular assemblies allows prediction of potential structures in related cases. The combination of detailed symmetry considerations with the basic rules of coordination chemistry has only recently allowed for the design of rational strategies for the construction of a variety of nanosized spherical containers, bowls, 1D-, 2D-, and 3D-coordination polymers with specified size and shape. PMID:22160460

  11. Formation of Highly Thermostable Copper-Containing Energetic Coordination Polymers Based on Oxidized Triaminoguanidine.

    PubMed

    Yan, Qi-Long; Cohen, Adva; Petrutik, Natan; Shlomovich, Avital; Zhang, Jian-Guo; Gozin, Michael

    2016-08-24

    A series of novel highly thermostable energetic coordination polymers (ECPs), with promising mechanical sensitivity properties, were prepared by an in situ oxidation-coordination reaction of triaminoguanidine hydrochloride with copper nitrate in aqueous solution. The molecular structures and properties of these ECPs could be tuned, by varying the ratios and concentrations of the starting materials. Our ECPs exhibit remarkable thermostability (>390 °C) and very low sensitivity to impact (Im > 98 J). The best-performing material (ECP-5) has a calculated detonation velocity of 8969 m·s(-1) and a decomposition peak temperature of 396.9 °C, demonstrating an outstanding balance between two inherently contradicting properties: high detonation performance and very low sensitivity.

  12. Formation of Highly Thermostable Copper-Containing Energetic Coordination Polymers Based on Oxidized Triaminoguanidine.

    PubMed

    Yan, Qi-Long; Cohen, Adva; Petrutik, Natan; Shlomovich, Avital; Zhang, Jian-Guo; Gozin, Michael

    2016-08-24

    A series of novel highly thermostable energetic coordination polymers (ECPs), with promising mechanical sensitivity properties, were prepared by an in situ oxidation-coordination reaction of triaminoguanidine hydrochloride with copper nitrate in aqueous solution. The molecular structures and properties of these ECPs could be tuned, by varying the ratios and concentrations of the starting materials. Our ECPs exhibit remarkable thermostability (>390 °C) and very low sensitivity to impact (Im > 98 J). The best-performing material (ECP-5) has a calculated detonation velocity of 8969 m·s(-1) and a decomposition peak temperature of 396.9 °C, demonstrating an outstanding balance between two inherently contradicting properties: high detonation performance and very low sensitivity. PMID:27483139

  13. 1D coordination polymers with polychalcogenides as linkers between metal atoms

    SciTech Connect

    Kysliak, Oleksandr; Beck, Johannes

    2013-07-15

    The reactions of zinc metal with elemental selenium and selenium/sulfur mixtures in liquid ammonia or methylamine under solvothermal conditions in closed glass ampoules at 50 °C lead within some days specifically to [Zn(NH{sub 3}){sub 2}Se{sub 4}]{sub n} (1), [Zn(MeNH{sub 2}){sub 2}Se{sub 4}]{sub n} (2), [Zn(NH{sub 3}){sub 2}Se{sub 2.23}S{sub 1.77}]{sub n} (3). From MnCl{sub 2}, Rb{sub 2}Se and excess Se in n-butylamine [Mn({sup n}BuNH{sub 2}){sub 4}Se{sub 6}]{sub n} (4) is obtained after prolonged reaction time at ambient temperature. The compounds are sensitive towards air and loss of NH{sub 3} or the amine ligands. The crystal structures were determined by single crystal diffraction at low temperatures. As a common structural feature, all compounds represent 1D coordination polymers with polychalcogenide chains as linkers between the metal atoms and consist of infinite [M–Ch{sub m}–]{sub n} chains (M=Zn, Mn; Ch{sub m}=Se{sub 4}, (S/Se){sub 4}, Se{sub 6}). The Zn central atoms in 1–3 have tetrahedral coordination with two amine ligands, the Mn atoms in 4 have octahedral coordination with four amine ligands and cis position of the two Se atoms. Raman spectra of 1–3 show the stretching mode vibrations of the Ch{sub 4} groups. The observation of S–S, S–Se, and Se–Se vibration bands in the spectrum of 3 indicates the presence of mixed S/Se polyanions. An optical band gap of 1.86(5) eV was determined for 2 by diffuse reflectance spectroscopy. - Graphical abstract: The reaction of Zn and Se in liquid methylamine yields dark red [Zn(NH{sub 2}CH{sub 3})Se{sub 4}], a 1D coordination polymer consisting of helical Zn–Se{sub 4}–Zn– chains. - Highlights: • A series of 1D coordination polymers consisting of metal amine complexes concatenated by polychalcogenide ions is presented. • Syntheses were performed as solvothermal reactions in liquid ammonia, liquid methylamine and n-butylamine. • Crystal structures are dominated by helices [M–Ch{sub m

  14. Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

    SciTech Connect

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-Li

    2013-09-15

    Three new metal-organic coordination polymers [Co(4-bbc){sub 2}(bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H{sub 2}O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H{sub 2}pdc=3,5-pyridinedicarboxylic acid, 1,4-H{sub 2}ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co{sup II} ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3{sup 2}·4·5·6{sup 2}·7{sup 4}) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphical abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated.

  15. Yttrium-succinates coordination polymers: Hydrothermal synthesis, crystal structure and thermal decomposition

    SciTech Connect

    Amghouz, Zakariae; Roces, Laura; Garcia-Granda, Santiago; Garcia, Jose R.; Souhail, Badredine; Mafra, Luis; Shi, Fa-nian; Rocha, Joao

    2009-12-15

    New polymeric yttrium-succinates, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}, have been synthesized, and their structures (solved by single crystal XRD) are compared with that of Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.H{sub 2}O. Three compounds were obtained as single phases, and their thermal behaviour is described. - Graphical abstract: In the field of coordination polymers or MOF's, few studies report on the polymorphs of Ln(III)-succinic acid. Here, we describe the hydrothermal synthesis and structural characterization of two novel yttrium-succinates coordination polymers, respectively 2D and 3D, Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 4}.6H{sub 2}O and Y{sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}(H{sub 2}O){sub 2}.

  16. Facile fabrication of MIL-103(Eu) porous coordination polymer nanostructures and their sorption and sensing properties.

    PubMed

    Liu, Qing; Yang, Ji-Min; Guo, Fan; Jin, Li-Na; Sun, Wei-Yin

    2016-04-01

    Nano/microscale lanthanide porous coordination polymer MIL-103(Eu) [Eu(BTB)] (H3BTB = 4,4',4''-benzene-1,3,5-triyl-tribenzoic acid) crystals have been fabricated at room temperature by a facile, convenient and environmentally friendly method. The structures of the products were confirmed by powder X-ray diffraction, and the crystal morphologies, including microrods, nanorods and nanospheres, were characterized by scanning electron microscopy. It is found that the addition of sodium acetate and the concentration of the reactants have an important impact on the morphology and size of the MIL-103(Eu) crystals. Gas adsorption measurements reveal that the products show high specific surface areas among the rare earth based coordination polymers and the MIL-103(Eu) nanorods can selectively adsorb CO2 over N2 under ambient conditions. Furthermore, all the products exhibit red emission corresponding to the (5)D0→(7)F2 transition of the Eu(iii) ion, and MIL-103(Eu) nanorods display sensitive and selective sensing for Cu(ii) ions and acetone molecules in solution.

  17. Syntheses, crystal structures, and properties of new metal--5-bromonicotinate coordination polymers

    NASA Astrophysics Data System (ADS)

    Li, Wenjie; Li, Guoting; Lv, Lulu; Zhao, Hong; Wu, Benlai

    2015-05-01

    Four metal-5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic)2(H2O)2]n (1), [Ni(Brnic)2]n (2), [Ni(Brnic)(bpy)(H2O)2]n·n(Brnic)·4.5nH2O (3), and [Co2(Brnic)3(bpy)2(OH)]n·nH2O (4) have been synthesized and structurally characterized (bpy=4,4‧-bipyridine). Complex 1 has corrugated (4,4) sheets formed by μ-Brnic ligands and planar nodes Fe(II). As for 2-4, they all built up from Brnic-bridged dinuclear subunits, but have very different structure features. Complex 2 is a twin-like polymer with (4,4) layers formed by twin paddle-wheel [Ni2(Brnic)4] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni2(Brnic)2] and trigons [Co2(Brnic)3(OH)], 63-topological cationic layers with nanosized grids of 3 and chiral ladder-type double chains of 4 formed, respectively. Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules 1-4. The thermostabilities of all compounds have been discussed in detail. Moreover, the magnetic investigations of 2 and 4 indicate that there exist antiferromagnetic interactions in the paddle-wheel [Ni2(Brnic)4] and trigon [Co2(Brnic)3(OH)] cores, respectively.

  18. Four coordination polymers derived from a one-pot reaction and their controlled synthesis.

    PubMed

    Yan, Wei; Hao, Han; Zheng, Hegen

    2016-04-21

    Four different Co(ii) coordination polymers have been built by two flexible ligands 4,4'-dicarboxydiphenyl sulfone (4,4'-sdb) and 1,4-bis((1H-imidazol-1-yl)methyl) benzene (BMB) in a one-pot solvothermal reaction. The structures of and are new, and and have been reported. The crystal structures of were obtained, namely [Co(4,4'-sdb)(BMB)]n (), {[Co2(4,4'-sdb)2(BMB)]·2H2O}n (), and [Co3(4,4'-sdb)2(DMF)(H2O)3]n (), but was confirmed by PXRD. Both and are 2D layered structures with sql topology and their point symbol is {4(4)·6(2)}. These complexes have been characterized by single crystal X-ray diffraction, infrared spectroscopy, thermogravimetry, elemental analysis, and powder X-ray diffraction measurements. By changing the synthesis conditions, four different Co(ii) coordination polymers can be obtained respectively. PMID:26948000

  19. Utilization of mixed ligands to construct two new coordination polymers: Syntheses, structures and properties

    NASA Astrophysics Data System (ADS)

    Wang, Yansong; Zhou, Zhimin

    2015-08-01

    The use of triazine and aromatic carboxylic acid as mixed chelating ligands in preparing two coordination polymers is described. Two new transition-metal coordination polymers, namely, [Co2(bpdc)4(phdat)2] (1) and [Zn(bpdc)]n (2) (H2bpdc=2,4-biphenyldicarboxylic acid, phdat=2,4-diamine-6-phenyl-1,3,5-triazine), have been hydrothermally synthesized and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. Compound 1 is a 0D structure and extends to a 3D network by two different N-H···O and N-H···N hydrogen bonds. Compound 2 exhibits a 2D network with 44.62 topological net, which contains two kinds of single helical chains. The interactions within each Co(II)-Co(II) pair of compound 1 are antiferromagnetic (g=2.19, J=-22 K, zj‧=-0.00351 K). Furthermore, the photoluminescence property of 2 was also investigated in the solid state at room temperature.

  20. Supramolecular self-assembly of 1D and 3D heterometallic coordination polymers with triruthenium building blocks.

    PubMed

    Chan, Sharon Lai-Fung; Gao, Song; Chui, Stephen Sin-Yin; Shek, Lam; Huang, Jie-Sheng; Che, Chi-Ming

    2012-09-01

    Ru(3)(TSA)(6) (1; H(2)TSA=2-thiosalicylic acid), which bears six peripheral carboxylate groups and was isolated in the form [NEt(4)](1.5)[Ru(3)(HTSA)(2)(TSA)(4)](OAc)(0.5)·3.5H(2)O, serves as a building block for assembly of heterometallic coordination polymers. Treatment of 1 with [Fe(acac)(3)] (acac=acetylacetonate) in EG/H(2)O (EG=ethylene glycol) afforded 1D Ru(3)-Fe coordination polymer 2 by means of the connection of the building block 1 through iron centers. Treatment of 1 with MnCl(2) in EG resulted in the formation of 1D Ru(3)-Mn(3) coordination polymer 3, which features self-assembled polynuclear linking units Mn(3)(OCH(2)CH(2)O)(3), each of which contains a planar Mn(3)O(3) ring. By treating 1 with Gd(NO(3))(3) and NaHCO(3) in EG, a 3D Ru(3)-Gd(6) coordination polymer 4 was obtained; this 3D coordination polymer features unprecedented Gd(6)(μ(3)-CO(3))(4) units. The magnetic properties of 1-4, along with DFT calculations on the electronic structure of 1, are also described.

  1. Spectroscopic properties of a series of Co(II) coordination polymers and the influence of Co(II) coordination environment on photoelectric property

    NASA Astrophysics Data System (ADS)

    Jin, Jing; Gong, Yuanyuan; Li, Lei; Han, Xiao; Meng, Qin; Liu, Yonghua; Niu, Shuyun

    2015-02-01

    Four Co(II) coordination polymers, [Co(suc)]n1, [Co(pdc)]n2, {[Co7(suc)4(OH)6(H2O)3] · 8H2O}n3, {[Co(bdc)(phen)(H2O)] · H2O}n4 (H2suc = succinic acid, H2pdc = pyridine-3,4-dicarboxylic acid, H2bdc = 1,2-benzenedicarboxylic acid, phen = 1,10-phenanthroline) were hydrothermally synthesized and characterized by X-ray single-crystal diffraction, surface photovoltage spectroscopy (SPS), electrical conductivity, thermogravimetric analysis (TG), ultraviolet visible and near-infrared absorption spectrum (UV-Vis-NIR), infrared spectrum (IR), and elemental analysis. The structural analyses indicate that the coordination numbers of the Co(II) ions are 4, 5, 6 and 6 for the polymers 1-4, respectively. And polymers 1 and 2 exhibit 3D structure formed by suc2- and pdc2- anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc2- anions bridging seven-nuclear [Co7(OH)6(H2O)3]3- unit and polymer 4 is a 1D structure bridged by bdc2- anions. The surface photoelectric properties of the cobalt polymers were mainly studied by SPS. The results of SPS reveal that all polymers possess certain photoelectric conversion property in the range of 300-800 nm. The influences of the structure, coordination micro-environment of central metal ion and structural dimensionality on response bands of SPS were discussed.

  2. Spectroscopic properties of a series of Co(II) coordination polymers and the influence of Co(II) coordination environment on photoelectric property.

    PubMed

    Jin, Jing; Gong, Yuanyuan; Li, Lei; Han, Xiao; Meng, Qin; Liu, Yonghua; Niu, Shuyun

    2015-02-25

    Four Co(II) coordination polymers, [Co(suc)]n 1, [Co(pdc)]n 2, {[Co7(suc)4(OH)6(H2O)3]·8H2O}n 3, {[Co(bdc)(phen)(H2O)]·H2O}n 4 (H2suc=succinic acid, H2pdc=pyridine-3,4-dicarboxylic acid, H2bdc=1,2-benzenedicarboxylic acid, phen=1,10-phenanthroline) were hydrothermally synthesized and characterized by X-ray single-crystal diffraction, surface photovoltage spectroscopy (SPS), electrical conductivity, thermogravimetric analysis (TG), ultraviolet visible and near-infrared absorption spectrum (UV-Vis-NIR), infrared spectrum (IR), and elemental analysis. The structural analyses indicate that the coordination numbers of the Co(II) ions are 4, 5, 6 and 6 for the polymers 1-4, respectively. And polymers 1 and 2 exhibit 3D structure formed by suc(2-) and pdc(2-) anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc(2-) anions bridging seven-nuclear [Co7(OH)6(H2O)3](3-) unit and polymer 4 is a 1D structure bridged by bdc(2-) anions. The surface photoelectric properties of the cobalt polymers were mainly studied by SPS. The results of SPS reveal that all polymers possess certain photoelectric conversion property in the range of 300-800 nm. The influences of the structure, coordination micro-environment of central metal ion and structural dimensionality on response bands of SPS were discussed.

  3. Spectroscopic properties of a series of Co(II) coordination polymers and the influence of Co(II) coordination environment on photoelectric property.

    PubMed

    Jin, Jing; Gong, Yuanyuan; Li, Lei; Han, Xiao; Meng, Qin; Liu, Yonghua; Niu, Shuyun

    2015-02-25

    Four Co(II) coordination polymers, [Co(suc)]n 1, [Co(pdc)]n 2, {[Co7(suc)4(OH)6(H2O)3]·8H2O}n 3, {[Co(bdc)(phen)(H2O)]·H2O}n 4 (H2suc=succinic acid, H2pdc=pyridine-3,4-dicarboxylic acid, H2bdc=1,2-benzenedicarboxylic acid, phen=1,10-phenanthroline) were hydrothermally synthesized and characterized by X-ray single-crystal diffraction, surface photovoltage spectroscopy (SPS), electrical conductivity, thermogravimetric analysis (TG), ultraviolet visible and near-infrared absorption spectrum (UV-Vis-NIR), infrared spectrum (IR), and elemental analysis. The structural analyses indicate that the coordination numbers of the Co(II) ions are 4, 5, 6 and 6 for the polymers 1-4, respectively. And polymers 1 and 2 exhibit 3D structure formed by suc(2-) and pdc(2-) anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc(2-) anions bridging seven-nuclear [Co7(OH)6(H2O)3](3-) unit and polymer 4 is a 1D structure bridged by bdc(2-) anions. The surface photoelectric properties of the cobalt polymers were mainly studied by SPS. The results of SPS reveal that all polymers possess certain photoelectric conversion property in the range of 300-800 nm. The influences of the structure, coordination micro-environment of central metal ion and structural dimensionality on response bands of SPS were discussed. PMID:25280332

  4. Tetrametallic lanthanide(III) phosphonate cages: synthetic, structural and magnetic studies.

    PubMed

    Zangana, Karzan H; Pineda, Eufemio Moreno; Winpenny, Richard E P

    2014-12-01

    The synthesis, structures and magnetic properties of a family of lanthanide complexes containing phosphonate ligands are reported. Reaction of hydrated lanthanide nitrate and (t)butylphosphonic acid under reflux conditions in iso-butanol, in the presence of pivalic acid as a co-ligand produced five new lanthanide complexes; pyridine (py) was present as a base. The compounds formed are tetrametallic, with the general formula [pyH]4[Ln4(μ3-OH)(O3P(t)Bu)3(HO3P(t)Bu)(O2C(t)Bu)2(NO3)6] where Ln = Gd(III), 1; Tb(III), 2; Dy(III), 3; Ho(III), 4 and Er(III), 5. The metal sites within the complexes lie on the vertices of a triangle-based pyramid, with phosphonate ligands on the triangular faces linking the apical Ln site to the Ln sites in the base. Each lanthanide(III) site is eight-coordinate. Magnetic studies of the compounds show a decline in the product χ(M)T with T; modelling the behaviour of 1 shows anti-ferromagnetic exchange between Gd(III) centres within the triangle with a negligible interaction to the fourth Gd(III) centre at the apex of the trigonal pyramid. PMID:25310820

  5. Utilization of mixed ligands to construct two new coordination polymers: Syntheses, structures and properties

    SciTech Connect

    Wang, Yansong; Zhou, Zhimin

    2015-08-15

    The use of triazine and aromatic carboxylic acid as mixed chelating ligands in preparing two coordination polymers is described. Two new transition-metal coordination polymers, namely, [Co{sub 2}(bpdc){sub 4}(phdat){sub 2}] (1) and [Zn(bpdc)]{sub n} (2) (H{sub 2}bpdc=2,4-biphenyldicarboxylic acid, phdat=2,4-diamine-6-phenyl-1,3,5-triazine), have been hydrothermally synthesized and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. Compound 1 is a 0D structure and extends to a 3D network by two different N–H···O and N–H···N hydrogen bonds. Compound 2 exhibits a 2D network with 4{sup 4}.6{sup 2} topological net, which contains two kinds of single helical chains. The interactions within each Co(II)–Co(II) pair of compound 1 are antiferromagnetic (g=2.19, J=−22 K, zj′=−0.00351 K). Furthermore, the photoluminescence property of 2 was also investigated in the solid state at room temperature. - Graphical abstract: Two polymeric metal compounds based on mixed-ligands were synthesized and characterized. The use of different metal ions results in distinct structures. The magnetic and fluorescent properties were also studied. - Highlights: • The first bpdc{sup 2−}/phdat-based 0D discrete coordination complex. • A new 2D architecture with two kinds of helical chains. • The structure-dependent magnetism and photoluminescence properties.

  6. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    NASA Astrophysics Data System (ADS)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-10-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg2+, Ca2+ and Ba2+) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO)4, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (44·62)3(49·66)2. The calcium compound consists of 1D infinite "Ca-O" inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D "Ba-O" inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions' influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies.

  7. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination.

    PubMed

    Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

    2016-03-17

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg(2+) detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb(3+) from the quenching effect of O-H vibration in water molecules. The subsequent addition of Hg(2+) into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg(2+). As a kind of Hg(2+) nanosensor, the probe exhibited excellent selectivity for Hg(2+) and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg(2+) in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. PMID:26920783

  8. One- and three-dimensional silver(I)-5-sulfosalicylate coordination polymers having ligand-supported and unsupported argentophilic interactions

    SciTech Connect

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Yeşilöz, Yeşim; Şahin, Onur

    2014-12-15

    Four new coordination polymers, namely, (Hemim·[Ag(Hssa)(H{sub 2}O)]){sub n} (1), ([Ag(ina){sub 2} Ag(Hssa)]·CH{sub 3}OH·H{sub 2}O){sub n} (2), ([Ag{sub 2}(Hssa)(dmp){sub 1.5}]·2H{sub 2}O){sub n} (3) and [Ag{sub 2}(Hssa)(daoc)]{sub n} (4) (Hssa: 5-Sulfosalicylate, emim: 2-ethyl-4-methylimidazole, ina: isonicotinamide, dmp: 2,5-dimethylpyrazine and daoc: 1,8-diaminooctane) were synthesized and characterized by IR spectroscopy, elemental analysis, single crystal X-ray diffraction, powder X-ray diffraction (PXRD) and thermal analysis techniques. Complexes 1 and 2 are one-dimensional (1D) coordination polymers while complexes 3 and 4 are three-dimensional (3D) coordination polymers. Complex 3 consists of three dimensional (3D) 3,3,6-c net with 3,3,6T37 topology. Complex 4 exhibits a 2-fold interpenetrating 3D framework with tfc topology. Complexes 1–4 contain ligand-supported (1–3) and unsupported (4) argentophilic Ag⋯Ag interactions. Photoluminescence spectra of the complexes demonstrate that photoluminescent properties may be attributed to intraligand transition of coordinated Hssa ligand. - Graphical abstract: In this study, four new Ag(I)-coordination polymers with 5-sulfosalicylate and some N-donor ligands were synthesized and characterized. Complexes 1 and 2 are one-dimensional (1D) coordination polymers while complexes 3 and 4 are three-dimensional (3D) coordination polymers. Complex 3 consists of three dimensional (3D) 3,3,6-c net with 3,3,6T37 topology. Complex 4 exhibits a 2-fold interpenetrating 3D framework with tfc topology. The complexes 1–4 contain ligand-supported (1–3) and unsupported (4) argentophilic Ag⋯Ag interactions. Photoluminescence spectra of the complexes demonstrated that photoluminescent properties may be attributed to intraligand transition of coordinated Hssa ligand. - Highlights: • Four novel Ag(I)-coordination polymers with 5-sulfosalicylate and N-donor ligands. • Complexes 1–4 contain ligand-supported (1–3) and

  9. Electrochemical Li-Ion Intercalation in Octacyanotungstate-Bridged Coordination Polymer with Evidence of Three Magnetic Regimes.

    PubMed

    Long, Jérôme; Asakura, Daisuke; Okubo, Masashi; Yamada, Atsuo; Guari, Yannick; Larionova, Joulia

    2016-08-01

    Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)5[W(CN)8] operates as a Li(+)-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li(+) ion in the solid-state redox reaction between paramagnetic [W(V)(CN)8](3-) and diamagnetic [W(IV)(CN)8](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved. PMID:27420412

  10. A visual and reversible assay for temperature using thioflavin T-doped lanthanide/nucleotide coordination polymers.

    PubMed

    Li, Yan-Yun; Jiang, Xiao-Qin; Zhang, Min; Shi, Guoyue

    2016-04-21

    In this work, we prepared a type of thioflavin T (ThT)-doped lanthanide/nucleotide coordination polymer by the self-assembly of ThT, europium ions (Eu(3+)) and nucleotides (guanosine monophosphate, GMP) in aqueous solution (i.e. ThT/Eu/GMP). The Eu/GMP coordination polymers show excellent adaptive inclusion properties for ThT in a convenient one-step approach, which can readily enhance the fluorescence of ThT via the restricted effect. Moreover, the as-prepared hydrophilic ThT/Eu/GMP coordination polymers have the capability to act as a temperature-sensitive, visual and reversible sensor in aqueous solution under the irradiation of visible light. Our proposed design is cost-effective and simple to prepare without chemical modification or fluorescence labeling. PMID:27010102

  11. Electrochemical Li-Ion Intercalation in Octacyanotungstate-Bridged Coordination Polymer with Evidence of Three Magnetic Regimes.

    PubMed

    Long, Jérôme; Asakura, Daisuke; Okubo, Masashi; Yamada, Atsuo; Guari, Yannick; Larionova, Joulia

    2016-08-01

    Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)5[W(CN)8] operates as a Li(+)-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li(+) ion in the solid-state redox reaction between paramagnetic [W(V)(CN)8](3-) and diamagnetic [W(IV)(CN)8](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved.

  12. In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers.

    PubMed

    Ghani, Milad; Frizzarin, Rejane M; Maya, Fernando; Cerdà, Víctor

    2016-07-01

    Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni-Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15-0.35μgL(-1). The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD's, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6-11.2%. Enrichment factors of 15-21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7-95.3%.

  13. New 3-D coordination polymers based on semi-rigid V-shape tetracarboxylates

    SciTech Connect

    Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning; Yu, Jie-Hui; Zhang, Ping; Xu, Ji-Qing

    2015-03-15

    Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N′-donor ligands yielded three new coordination polymers as [Cu{sub 4}(fph){sub 2}(bpe){sub 3}(H{sub 2}O){sub 2}]·2H{sub 2}O (fph=4,4′-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co{sub 2}(fph)(bpa){sub 2}(H{sub 2}O){sub 2}]·3H{sub 2}O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H{sub 2}O)(H{sub 2}oph)(bpa)] (oph=4,4′-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu{sup 2+} ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co{sup 2+} ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1–3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors. - Graphical abstract: Structures of three semi-rigid V-shape tetracarboxylate-based coordination polymers were reported, and their magnetic properties were investigated. - Highlights: • Structures of three tetracarboxylate-based coordination polymers were reported. • Role of organic bases in metal–tetracarboxylate compounds was discussed. • Characters of V-shape and semi-rigidity for tetracarboxylate play a key role in crystal growth. • Their magnetic properties were investigated.

  14. Isostructural 1D coordination polymers of Zn(II), Cd(II) and Cu(II) with phenylpropynoic acid and DABCO as organic linkers

    NASA Astrophysics Data System (ADS)

    Saravanakumar, Rajendran; Varghese, Babu; Sankararaman, Sethuraman

    2014-11-01

    Using phenylpropynoic acid (PPA) and 1,4-diazabicyclo[2.2.2]octane (DABCO) as organic spacers, isostructural coordination polymers of Zn(II), Cd(II) and Cu(II) were synthesized by solvothermal method and structurally characterized using single crystal XRD, powder XRD, 13C CP-MAS NMR spectroscopy. Single crystal XRD data revealed four PPA units coordinating with two metal ions forming a paddle wheel secondary building unit (SBU). The paddle wheel units are connected through coordination of DABCO nitrogen to the metal centers from the axial positions leading to the formation of the 1D coordination polymers along the c axis. Intermolecular π stacking and Csbnd H…π interactions between the adjacent polymer chains convert the 1D coordination polymer into an interesting 3D network with the Csbnd H…π bonds running along the crystallographic a and b axes. Thermal and nitrogen adsorption studies of these coordination polymers are reported.

  15. Two new luminescent Zn(II) coordination polymers with different interpenetrated motifs

    NASA Astrophysics Data System (ADS)

    Song, Changying; Liu, Qifeng; Liu, Wei; Cao, Ziqing; Ren, Yuanyuan; Zhou, Qichao; Zhang, Li

    2015-11-01

    Solvothermal reactions of Zn(NO3)2, H2tdc and bib in the presence of different solvents (DMF = N,N'- dimethylformamide or DMA = N,N'- dimethylacetamide) have given rise to two new coordination polymers, namely [Zn2(tdc)2(bib)2]n·2n(H2O) (1) and [Zn(tdc)(bib)0.5(H2O)]n (2) (H2tdc = 2,5-thiophenedicarboxylic acid, bib = 1, 4-bis(imidazolyl)butane). The structures were determined by single crystal X-ray diffraction and characterized by elemental analysis, powder X-ray diffraction and infrared spectroscopy. Compound 1 exhibits a 4-fold interpenetrated dia topological network, and compound 2 features a 8-fold interpenetrated ths topological network. In addition, thermal stabilities and solid state luminescent properties of these two compounds were also investigated.

  16. A Highly Water-Tolerant Magnesium(II) Coordination Polymer Derived from a Flexible Layered Structure.

    PubMed

    Ochi, Rika; Noro, Shin-Ichiro; Kamiya, Yuichi; Kubo, Kazuya; Nakamura, Takayoshi

    2016-07-25

    A two-dimensional (2D) layered Mg(II) coordination polymer (CP) with a high tolerance for H2 O was designed, synthesised, and crystallographically characterised. The synthesis was achieved by the introduction of a flexible 2D layered structure composed of Mg(II) ions and isonicotinate N-oxide ligands. Owing to its high H2 O tolerance, the obtained 2D layered structure has the flexibility to repeatedly adsorb a large amount of H2 O associated with interlayer expansion and enable the removal of H2 O from a H2 O/2-propanol mixed vapour. These results indicate that the CP could be an excellent dehydrating agent. PMID:27373696

  17. Coordination polymer core/shell structures: Preparation and up/down-conversion luminescence.

    PubMed

    Li, Bingmei; Xu, Hualan; Xiao, Chen; Shuai, Min; Chen, Weimin; Zhong, Shengliang

    2016-10-01

    Coordination polymer (CP) core-shell nanoparticles with Gd-based CP (GdCP) as core and Eu-based CP (EuCP) as shell have been successfully prepared. Allantoin was employed as the organic building block without the assistance of any template. The composition, size and structure of the core-shell nanospheres were well characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TG). Results show that the resultant cores are uniform nanospheres with diameter of approximately 45nm, while the diameters of the core-shell nanospheres are increased to approximately 60nm. The core-shell products show enhanced luminescence efficiency than the core under 980nm laser excitation and decreased down-conversion luminescence when excited at 394nm.

  18. Catalytic glucose isomerization by porous coordination polymers with open metal sites.

    PubMed

    Akiyama, George; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu

    2014-10-01

    Highly efficient catalytic isomerization reactions from glucose to fructose in aqueous media using porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is reported for the first time. The catalytic activity of PCPs functionalized with -NH2, -(CH3)2, -NO2, and -SO3H groups on the pore surface is systematically tested. The catalytic activity can be tuned by the acidity of open metal sites (OMSs) by modifying the organic linkers with the functional groups. As a result, it is demonstrated that MIL-101 functionalized with -SO3H not only shows high conversion of glucose but also selectively produces fructose. Further, catalytic one-pot conversion of amylose to fructose is achieved, thanks to the high stability of the framework in an acidic solution. These results show that MOF/PCP compounds having OMSs are promising materials for various useful heterogeneous catalytic reactions, in particular in the biomass field. PMID:25080129

  19. Pressure Sensor via Optical Detection Based on a 1D Spin Transition Coordination Polymer

    PubMed Central

    Jureschi, Cătălin M.; Linares, Jorge; Rotaru, Aurelian; Ritti, Marie Hélène; Parlier, Michel; Dîrtu, Marinela M.; Wolff, Mariusz; Garcia, Yann

    2015-01-01

    We have investigated the suitability of using the 1D spin crossover coordination polymer [Fe(4-(2′-hydroxyethyl)-1,2,4-triazole)3]I2·H2O, known to crossover around room temperature, as a pressure sensor via optical detection using various contact pressures up to 250 MPa. A dramatic persistent colour change is observed. The experimental data, obtained by calorimetric and Mössbauer measurements, have been used for a theoretical analysis, in the framework of the Ising-like model, of the thermal and pressure induced spin state switching. The pressure (P)-temperature (T) phase diagram calculated for this compound has been used to obtain the P-T bistability region. PMID:25621610

  20. A systematic study on the stability of porous coordination polymers against ammonia.

    PubMed

    Kajiwara, Takashi; Higuchi, Masakazu; Watanabe, Daisuke; Higashimura, Hideyuki; Yamada, Teppei; Kitagawa, Hiroshi

    2014-11-17

    To establish a strategy for designing porous coordination polymers (PCPs) for ammonia capture, the first systematic study on the stability of PCPs against ammonia was conducted. Various types of PCPs were investigated by comparing their powder XRD patterns before and after treatment with ammonia. Among the PCPs tested, ZIF-8, MIL-53(Al), Al-BTB, MOF-76(M) (M=Y or Yb), MIL-101(Cr), and MOF-74(Mg) were stable up to 350 °C under an ammonia atmosphere at ambient pressure. The origin of the stability of PCPs is discussed from the viewpoint of their components, metal cations, and organic linkers. Furthermore, adsorption isotherm measurements show that the adsorptive behavior of PCPs is independent of their stability.

  1. Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

    NASA Astrophysics Data System (ADS)

    Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E.; Chan, Benny C.; de Lill, Daniel T.

    2015-05-01

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C6H2O5)(C6H3O5)(H2O)]n (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented.

  2. Coordination polymer core/shell structures: Preparation and up/down-conversion luminescence.

    PubMed

    Li, Bingmei; Xu, Hualan; Xiao, Chen; Shuai, Min; Chen, Weimin; Zhong, Shengliang

    2016-10-01

    Coordination polymer (CP) core-shell nanoparticles with Gd-based CP (GdCP) as core and Eu-based CP (EuCP) as shell have been successfully prepared. Allantoin was employed as the organic building block without the assistance of any template. The composition, size and structure of the core-shell nanospheres were well characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TG). Results show that the resultant cores are uniform nanospheres with diameter of approximately 45nm, while the diameters of the core-shell nanospheres are increased to approximately 60nm. The core-shell products show enhanced luminescence efficiency than the core under 980nm laser excitation and decreased down-conversion luminescence when excited at 394nm. PMID:27344485

  3. Flexible Two-Dimensional Square-Grid Coordination Polymers: Structures and Functions

    PubMed Central

    Kajiro, Hiroshi; Kondo, Atsushi; Kaneko, Katsumi; Kanoh, Hirofumi

    2010-01-01

    Coordination polymers (CPs) or metal-organic frameworks (MOFs) have attracted considerable attention because of the tunable diversity of structures and functions. A 4,4′-bipyridine molecule, which is a simple, linear, exobidentate, and rigid ligand molecule, can construct two-dimensional (2D) square grid type CPs. Only the 2D-CPs with appropriate metal cations and counter anions exhibit flexibility and adsorb gas with a gate mechanism and these 2D-CPs are called elastic layer-structured metal-organic frameworks (ELMs). Such a unique property can make it possible to overcome the dilemma of strong adsorption and easy desorption, which is one of the ideal properties for practical adsorbents. PMID:21152303

  4. Trapping of a spatial transient state during the framework transformation of a porous coordination polymer.

    PubMed

    Kondo, Mio; Furukawa, Shuhei; Hirai, Kenji; Tsuruoka, Takaaki; Reboul, Julien; Uehara, Hiromitsu; Diring, Stéphane; Sakata, Yoko; Sakata, Osami; Kitagawa, Susumu

    2014-04-01

    Structural transformability accompanied by molecular accommodation is a distinguished feature of porous coordination polymers (PCPs) among porous materials. Conventional X-ray crystallography allows for the determination of each structural phase emerged during transformation. However, the propagation mechanism of transformation through an entire crystal still remains in question. Here we elucidate the structural nature of the spatial transient state, in which two different but correlated framework structures, an original phase and a deformed phase, simultaneously exist in one crystal. The deformed phase is distinctively generated only at the crystal surface region by introducing large guest molecules, while the remaining part of crystal containing small molecules maintains the original phase. By means of grazing incidence diffraction techniques we determine that the framework is sheared with sharing one edge of the original primitive cubic structure, leading to the formation of crystal domains with four mirror image relationships.

  5. Structural optimization of interpenetrated pillared-layer coordination polymers for ethylene/ethane separation.

    PubMed

    Kishida, Keisuke; Horike, Satoshi; Watanabe, Yoshihiro; Tahara, Mina; Inubushi, Yasutaka; Kitagawa, Susumu

    2014-06-01

    With the goal of achieving effective ethylene/ethane separation, we evaluated the gas sorption properties of four pillared-layer-type porous coordination polymers with double interpenetration, [Zn2(tp)2(bpy)]n (1), [Zn2(fm)2(bpe)]n (2), [Zn2(fm)2(bpa)]n (3), and [Zn2(fm)2(bpy)]n (4) (tp = terephthalate, bpy = 4,4'-bipyridyl, fm = fumarate, bpe = 1,2-di(4-pyridyl)ethylene and bpa = 1,2-di(4-pyridyl)ethane). It was found that 4, which contains the narrowest pores of all of these compounds, exhibited ethylene-selective sorption profiles. The ethylene selectivity of 4 was estimated to be 4.6 at 298 K based on breakthrough experiments using ethylene/ethane gas mixtures. In addition, 4 exhibited a good regeneration ability compared with a conventional porous material.

  6. Pressure-induced amorphization of a dense coordination polymer and its impact on proton conductivity

    SciTech Connect

    Umeyama, Daiki; Hagi, Keisuke; Ogiwara, Naoki; Horike, Satoshi E-mail: kitagawa@icems.kyoto-u.ac.jp; Tassel, Cedric; Kageyama, Hiroshi; Higo, Yuji; Kitagawa, Susumu E-mail: kitagawa@icems.kyoto-u.ac.jp

    2014-12-01

    The proton conductivity of a dense coordination polymer (CP) was investigated under high-pressure conditions. Impedance measurements under high pressures revealed that the proton conductivity of the CP decreased more than 1000-fold at pressures of 3–7 GPa and that the activation energy for proton conduction almost doubled compared with that at ambient pressure. A synchrotron X-ray study under high pressure identified the amorphization process of the CP during compression, which rationally explains the decrease in conductivity and increase in activation energy. This phenomenon is categorized as reversible pressure-induced amorphization of a dense CP and is regarded as a demonstration of the coupling of the mechanical and electrical properties of a CP.

  7. Synthesis, crystal structure and photoluminescent properties of four lanthanide 5-nitroisophthalate coordination polymers

    SciTech Connect

    Huang Yan; Yan Bing; Shao Min

    2009-04-15

    Four new lanthanide coordination polymers, [Y(Hnip)(nip)(H{sub 2}O)].H{sub 2}O (1), [Ln(Hnip)(nip)(H{sub 2}O){sub 2}].2H{sub 2}O [Ln=Eu(2), Tb(3)] and [Y(nip){sub 2}].(H{sub 2}4,4'-bpy){sub 0.5} (4) [5-nip=5-nitroisophthalate, 4,4'-bpy=4,4'-bipyridine], have been hydrothermally synthesized and structurally characterized. Compound 1 features novel lanthanide-carboxylate groups chains composed of three samehanded helical strands intersecting each other through hinged lanthanide atoms, and these chains are cross-linked by phenylene moieties of carboxylate ligands into a 2D layer structure. Compounds 2 and 3 are isomorphous, and contain 1D catenanelike Ln-O-C-O-Ln chains, which are interconnected by phenylene moieties into 2D layer structures. Compound 4, however, displays a 3D architecture sustained by strong hydrogen bonding interactions between the protonated 4,4'-bpy and the carboxyl oxygen atom from [Y{sub 2}(nip){sub 4}]{sup 2-} with 2D layer structure, and 4,4'-bpy as the guest molecules exist in bilayer channel. The studies for the thermal stabilities of the four compounds show that compound 4 is more stable than other compounds. Compound 2 emits characteristic red luminescence of Eu{sup 3+} ions at room temperature, and its luminescent lifetime and quantum efficiency has been determined. - Graphical abstract: Four lanthanide 5-nitroisophthalate coordination polymers have been hydrothermally prepared and resent different structures and thermal stabilities and photoluminescence properties.

  8. Electrical conductivity and luminescence properties of two silver(I) coordination polymers with heterocyclic nitrogen ligands

    SciTech Connect

    Rana, Abhinandan; Kumar Jana, Swapan; Pal, Tanusri; Puschmann, Horst; Zangrando, Ennio; Dalai, Sudipta

    2014-08-15

    The synthesis and X-ray structural characterization of two novel silver(I) coordination polymers, [Ag(NO{sub 3})(quin)]{sub n} (1) and [Ag{sub 8}(HL){sub 2}(H{sub 2}O){sub 4}(mpyz)]·3H{sub 2}O (2) are reported, where quin=5,6,7,8-tetrahydroquinoxaline, H{sub 6}L=cyclohexane-1,2,3,4,5,6-hexacarboxylic acid and mpyz=2-methyl pyrazine. The single crystal diffraction analyses showed that complex 1 is a 2D layered structure, while 2 presents a 3D polymeric architecture. In complex 2 the network is stabilized by argentophilic interactions and hydrogen bonding. Electrical conductivity of order 3×10{sup −4} Scm{sup −1} (1) and 1.6×10{sup −4} Scm{sup −1} (2) is measured on thin film specimen at room temperature. The photoluminescence and thermal properties of the complexes have also been studied. - Graphical abstract: Two new 1D and 3D coordination polymers of Ag(I) have been synthesized and characterized by X-ray analysis. The electrical, luminescence and thermal properties have been studied. - Highlights: • 1 is 2D layered while 2 present a 3D polymeric architecture. • The network in 2 is stabilized by argentophilic interactions and hydrogen bonding. • Electrical conductivity measurement is quite interesting. • Argentophilic interaction and intra-ligand π{sup ⁎}–π CT explains emission behavior of 2.

  9. Lanthanide Coordination Polymer Nanoparticles as an Excellent Artificial Peroxidase for Hydrogen Peroxide Detection.

    PubMed

    Zeng, Hui-Hui; Qiu, Wei-Bin; Zhang, Li; Liang, Ru-Ping; Qiu, Jian-Ding

    2016-06-21

    Lanthanide coordination polymer nanoparticles (Ln-CPNs) have been recently demonstrated as excellent platforms for biomolecule detection. In this work, we synthesized novel cerium coordination polymer nanoparticles ATP-Ce-Tris CPNs in a simple and quick way using ATP molecules as the biocompatible ligands to Ce(3+) ions in tris(hydroxymethyl)aminomethane hydrochloric (Tris-HCl) solution. In view of the excellent free radical scavenging property of cerium compounds, which is ascribed to the mixed valence state (Ce(3+), Ce(4+)) and the reversible switch from Ce(3+) to Ce(4+), the synthesized ATP-Ce-Tris CPNs was used as artificial peroxidase to selectively and sensitively detect H2O2. The sensing mechanism depends on the oxidation of the fluorescent ATP-Ce(III)-Tris CPNs to nonfluorescent ATP-Ce(IV)-Tris CPNs by H2O2. Compared with those inorganic cerium oxide sensors, this kind of fluoresence ATP-Ce-Tris CPNs sensor needs no additional organic redox dye, such as ABTS (2,20-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid), TMB (3,3,5,5-tetramethylbenzidine), or fluorescein as signal molecules. Moreover, such ATP-Ce-Tris CPNs sensor exhibited a more sensitive response to H2O2 with a detection limit down to 0.6 nM, which is 2 orders of magnitude lower than those of cerium oxide sensors. This sensing platform was further extended to the detection of glucose in combination with the specific catalytic effect of glucose oxidase (GOx) for the oxidation of glucose and formation of H2O2. PMID:27220993

  10. Carboxyl group (-CO2 H) functionalized coordination polymer nanoparticles as efficient platforms for drug delivery.

    PubMed

    Novio, Fernando; Lorenzo, Julia; Nador, Fabiana; Wnuk, Karolina; Ruiz-Molina, Daniel

    2014-11-17

    Functionalization of nanoparticles can significantly influence their properties and potential applications. Although researchers can now functionalize metal, metal oxide, and organic polymer nanoparticles with a high degree of precision, controlled surface functionalization of nanoscale coordination polymer particles (CPPs) has remained a significant challenge. The lack of methodology is perhaps one of the greatest roadblocks to the advancement of CPPs into high added-value drug delivery applications. Here, we report having achieved this goal through a stepwise formation and functionalization protocol. We fabricated robust nanoparticles with enhanced thermal and colloidal stabilities by incorporation of carboxyl groups and these surface carboxyl groups could be subsequently functionalized through well-known peptide coupling reactions. The set of chemistries that we employed as proof-of-concept enabled a plethora of new functional improvements for the application of CPPs as drug delivery carriers, including enhanced colloidal stabilities and the incorporation of additional functional groups such as polyethylene glycol (PEG) or fluorescent dyes that enabled tracking of their cellular uptake. Finally, we ascertained the cytotoxicity of the new CPP nanoparticles loaded with camptothecin to human breast adenocarcinoma (MCF-7). Efflux measurements show that the encapsulation of camptothecin enhances the potency of the drug 6.5-fold and increases the drug retention within the cell. PMID:25284328

  11. Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide

    NASA Astrophysics Data System (ADS)

    Tran, Phong D.; Tran, Thu V.; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

    2016-06-01

    Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13]2- building blocks. Of the three terminal disulfide (S22-) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum.

  12. Carboxyl group (-CO2 H) functionalized coordination polymer nanoparticles as efficient platforms for drug delivery.

    PubMed

    Novio, Fernando; Lorenzo, Julia; Nador, Fabiana; Wnuk, Karolina; Ruiz-Molina, Daniel

    2014-11-17

    Functionalization of nanoparticles can significantly influence their properties and potential applications. Although researchers can now functionalize metal, metal oxide, and organic polymer nanoparticles with a high degree of precision, controlled surface functionalization of nanoscale coordination polymer particles (CPPs) has remained a significant challenge. The lack of methodology is perhaps one of the greatest roadblocks to the advancement of CPPs into high added-value drug delivery applications. Here, we report having achieved this goal through a stepwise formation and functionalization protocol. We fabricated robust nanoparticles with enhanced thermal and colloidal stabilities by incorporation of carboxyl groups and these surface carboxyl groups could be subsequently functionalized through well-known peptide coupling reactions. The set of chemistries that we employed as proof-of-concept enabled a plethora of new functional improvements for the application of CPPs as drug delivery carriers, including enhanced colloidal stabilities and the incorporation of additional functional groups such as polyethylene glycol (PEG) or fluorescent dyes that enabled tracking of their cellular uptake. Finally, we ascertained the cytotoxicity of the new CPP nanoparticles loaded with camptothecin to human breast adenocarcinoma (MCF-7). Efflux measurements show that the encapsulation of camptothecin enhances the potency of the drug 6.5-fold and increases the drug retention within the cell.

  13. Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide.

    PubMed

    Tran, Phong D; Tran, Thu V; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

    2016-06-01

    Molybdenum sulfides are very attractive noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) from water. The atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx), which exhibits significantly higher HER activity compared to its crystalline counterpart. Here we show that HER-active a-MoSx, prepared either as nanoparticles or as films, is a molecular-based coordination polymer consisting of discrete [Mo3S13](2-) building blocks. Of the three terminal disulfide (S2(2-)) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimization of this HER electrocatalyst as an alternative to platinum. PMID:26974410

  14. Tricarboxylate-based Gd(III) coordination polymers exhibiting large magnetocaloric effects.

    PubMed

    Liu, Sui-Jun; Cao, Chen; Xie, Chen-Chao; Zheng, Teng-Fei; Tong, Xiao-Lan; Liao, Jin-Sheng; Chen, Jing-Lin; Wen, He-Rui; Chang, Ze; Bu, Xian-He

    2016-05-31

    Two Gd(III) coordination polymers with the formula [Gd(cit)(H2O)]∞ () and [Gd(nta)(H2O)2]∞ () (H4cit = citric acid, H3nta = nitrilotriacetic acid) have been successfully prepared under hydrothermal conditions. Complex exhibits a three-dimensional (3D) structure based on carboxylate-bridged layers, while complex is a double-layer structure containing eight-coordinated Gd(III). Magnetic investigations reveal that weak antiferromagnetic couplings between adjacent Gd(III) ions in both and with different Weiss values result in large cryogenic magnetocaloric effects. It is notable that the maximum entropy changes (-ΔS) of and reach 31.3 J kg(-1) K(-1) and 32.2 J kg(-1) K(-1) at 2 K for a moderate field change (ΔH = 3 T), and a remarkable -ΔS (41.5 J kg(-1) K(-1) for and 42.0 J kg(-1) K(-1) for ) could be obtained for ΔH = 7 T.

  15. Gram-scale synthesis of coordination polymer nanodots with renal clearance properties for cancer theranostic applications

    PubMed Central

    Liu, Fuyao; He, Xiuxia; Chen, Hongda; Zhang, Junping; Zhang, Huimao; Wang, Zhenxin

    2015-01-01

    An ultrasmall hydrodynamic diameter is a critical factor for the renal clearance of nanoparticles from the body within a reasonable timescale. However, the integration of diagnostic and therapeutic components into a single ultrasmall nanoparticle remains challenging. In this study, pH-activated nanodots (termed Fe-CPNDs) composed of coordination polymers were synthesized via a simple and scalable method based on coordination reactions among Fe3+, gallic acid and poly(vinylpyrrolidone) at ambient conditions. The Fe-CPNDs exhibited ultrasmall (5.3 nm) hydrodynamic diameters and electrically neutral surfaces. The Fe-CPNDs also exhibited pH-activatable magnetic resonance imaging contrast and outstanding photothermal performance. The features of Fe-CPNDs greatly increased the tumour-imaging sensitivity and facilitated renal clearance after injection in animal models in vivo. Magnetic resonance imaging-guided photothermal therapy using Fe-CPNDs completely suppressed tumour growth. These findings demonstrate that Fe-CPNDs constitute a new class of renal clearable nanomedicine for photothermal therapy and molecular imaging. PMID:26245151

  16. Divergent layer topologies in divalent metal aliphatic dicarboxylate coordination polymers containing 3-pyridylmethylnicotinamide

    NASA Astrophysics Data System (ADS)

    White, Charmaine L.; Torres Salgado, Maria D.; Mizzi, Jessica E.; LaDuca, Robert L.

    2015-12-01

    Hydrothermal reaction of the requisite metal salt, an aliphatic dicarboxylic acid, and the hydrogen-bonding capable dipyridylamide ligand 3-pyridylmethylnicotinamide (3-pmna) resulted in four coordination polymers whose connectedness and layer topology depend on the metal coordination environment and dicarboxylate binding mode. These new crystalline phases were characterized by single crystal X-ray diffraction. [Cu(ox)(3-pmna)]n (1, ox = oxalate) manifests stacked 3-connected (6,3) herringbone layer motifs. {[Cd(mal)(3-pmna)(H2O)]·3H2O}n (2, mal = malonate) shows a 4-connected (4,4) grid topology with entrained water molecule trimeric chains in the interlamellar regions. {[Cd2(suc)2(3-pmna)(H2O)2]·3H2O}n (3, suc = succinate) possesses {Cd2O2} dimer-based [Cd(suc)]n layers pillared by 3-pmna ligands into a 5-connected sandwich motif with 4862 topology. {[Cd(glu)(3-pmna)(H2O)]·3H2O}n (4, glu = glutarate) manifests a rippled (4,4) grid topology. Luminescent behavior in the cadmium complexes is ascribed to intra-ligand molecular orbital transitions. Thermal decomposition behavior is also discussed herein.

  17. Gram-scale synthesis of coordination polymer nanodots with renal clearance properties for cancer theranostic applications

    NASA Astrophysics Data System (ADS)

    Liu, Fuyao; He, Xiuxia; Chen, Hongda; Zhang, Junping; Zhang, Huimao; Wang, Zhenxin

    2015-08-01

    An ultrasmall hydrodynamic diameter is a critical factor for the renal clearance of nanoparticles from the body within a reasonable timescale. However, the integration of diagnostic and therapeutic components into a single ultrasmall nanoparticle remains challenging. In this study, pH-activated nanodots (termed Fe-CPNDs) composed of coordination polymers were synthesized via a simple and scalable method based on coordination reactions among Fe3+, gallic acid and poly(vinylpyrrolidone) at ambient conditions. The Fe-CPNDs exhibited ultrasmall (5.3 nm) hydrodynamic diameters and electrically neutral surfaces. The Fe-CPNDs also exhibited pH-activatable magnetic resonance imaging contrast and outstanding photothermal performance. The features of Fe-CPNDs greatly increased the tumour-imaging sensitivity and facilitated renal clearance after injection in animal models in vivo. Magnetic resonance imaging-guided photothermal therapy using Fe-CPNDs completely suppressed tumour growth. These findings demonstrate that Fe-CPNDs constitute a new class of renal clearable nanomedicine for photothermal therapy and molecular imaging.

  18. Four homochiral coordination polymers contain N-acetyl-L-tyrosine and different N-donor ligand: Influence of metal cations, ancillary ligands and coordination modes

    SciTech Connect

    Li, Meng-Li; Song, Hui-Hua

    2013-10-15

    Using the chiral ligand N-acetyl-L-tyrosine (Hacty) and maintaining identical reaction conditions, Zn(II), Co(II), and Cd(II) salts provided four novel homochiral coordination polymers ([Zn(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}1, ([Co(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}2, ([Cd(acty){sub 2}(bipy)H{sub 2}O]·H{sub 2}O){sub n}3, and ([Cd(acty)(bpe){sub 2}(Ac)]·6H{sub 2}O){sub n}4 (bipy=4,4′-bipyridine; bpe=1,2-di(4-pyridyl)ethane) in the presence of ancillary ligands. Compounds 1 and 2 are isostructural 1D chain structures. The neighboring chains are further linked into a 3D supramolecular structure via π⋯π stacking and hydrogen bond interactions. Compound 3 shows a 2D network and 4 generates 1D infinite chains along the c-axis. Compounds 3 and 4 are further connected into 3D supramolecular network by hydrogen bond interactions. More importantly, coordination in acyl oxygen atoms and ancillary ligands (bpe) as monodentate decorating ligands in 4 are rarely reported. Ancillary ligands and metal cations significantly influence the structure of the complexes. The photoluminescence properties of 1, 3, and 4 were studied at room temperature. Circular dichroism (CD) of the complexes have been investigated. - Graphical abstract: Four new homochiral coordination polymers were prepared and structurally characterized, which investigate the influence of the ancillary ligands and metal ions on the design and synthesis of coordination polymers. Display Omitted - Highlights: • It is rarely reported that the chiral coordination polymers prepared with N-acetyl-L-tyrosine ligands. • The alkalescent acetyl oxygen atom is difficult to participate in coordination but it is happened in the N-acetyl-L-tyrosine ligands. • The ancillary ligands (4,4′-bipy and bpe) are present in an unusual coordination modes, monodentate decorating ligands in 1, 2 and 4. • Structure comparative analyses results indicate that the

  19. Phenylthiolate as a sigma- and pi- donor ligand: synthesis of a 3-D organometallic coordination polymer [K2Fe(SPh)4]n.

    PubMed

    Yu, Xiao-Yan; Jin, Guo-Xin; Weng, Lin-Hong

    2004-07-01

    The synthesis and crystal structure of the first mixed-metal organometallic polymer network containing phenylthiolato ligands, [K2Fe(SPh)4]n, are investigated. The simple phenylthiolate acts as a sigma- and pi-donor ligand to give a 3-D potassium iron coordination polymer with both metal-carbon and metal-sulfur coordination interactions.

  20. Enantioselective recognition and separation of racemic 1-phenylethanol by a pair of 2D chiral coordination polymers.

    PubMed

    Li, Zi-Jian; Yao, Jia; Tao, Qian; Jiang, Long; Lu, Tong-Bu

    2013-10-21

    A pair of 2D chiral coordination polymers were constructed through the self-assembly of a chiral metal-camphor-10-sulfonate salt and a bidentate linker, which show selective inclusion of S and R enantiomers of 1-phenylethanol respectively with an enantioselectivity of 9:1. PMID:24083956

  1. A 2D cobalt based coordination polymer constructed from benzimidazole and acetate ion exhibiting spin-canted antiferromagnetism.

    PubMed

    Arai, Leo; Nadeem, Muhammad Arif; Bhadbhade, Mohan; Stride, John Arron

    2010-04-14

    A coordination polymer, [Co(II)(bIM)(acetate)] (bIM = benzimidazole) was synthesized using a solvothermal method; the complex has a two dimensional non-interpenetrated network structure and exhibits a spin-canted antiferromagnetic behaviour at low temperature and a high coercive field.

  2. Nucleotide/Tb³⁺ coordination polymer nanoparticles as luminescent sensor and scavenger for nitrite ion.

    PubMed

    Qi, Zewan; You, Qi; Chen, Yang

    2016-01-01

    Newly emerged metal organic coordination polymers have aroused the great interest in designing tailored functional materials. In this study, multiple functional components, luminescent Tb(3+) ion, nucleobase and antenna molecule, were integrated in a single material and prepared into a responsive nanoparticle for nitrite. The terbium coordination polymer nanoparticles made of this kind of material have the dual functions of recognition and transduction and obey a preset sensing mechanism without a post-functionalization of common materials. As the result of the tailored, the terbium coordination polymer nanoparticles are highly sensitive and selective to nitrite by means of Dexter energy transfer between Tb(3+) ion and nitrite, and can be used for the scavenger for nitrite in aqueous solution. The detection limit, dynamic range and removal capacity of U-Tb-OBBA CPNPs for nitrite are 0.3 µM, 0.3-470 µM and 4.44 mg per gram of particles, respectively. Metal organic coordination polymers show an attractive potential in constructing smart sensing materials.

  3. Hydrothermal reactions: From the synthesis of ligand to new lanthanide 3D-coordination polymers

    SciTech Connect

    Silva, Fausthon Fred da; Fernandes de Oliveira, Carlos Alberto; Lago Falcão, Eduardo Henrique; Gatto, Claudia Cristina; Bezerra da Costa, Nivan; Oliveira Freire, Ricardo; Chojnacki, Jarosław; Alves Júnior, Severino

    2013-11-15

    The organic ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) was synthesized under hydrothermal conditions starting from the iminodiacetic acid and catalyzed by oxalic acid. The X-ray powder diffraction data indicates that the compound crystallizes in the P2{sub 1}/c monoclinic system as reported in the literature. The ligand was also characterized by elemental analysis, magnetic nuclear resonance, infrared spectroscopy and thermogravimetric analysis. Two new coordination networks based on lanthanide ions were obtained with this ligand using hydrothermal reaction. In addition to single-crystal X-ray diffraction, the compounds were characterized by infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and elemental analysis. Single-crystal XRD showed that the compounds are isostructural, crystallizing in P2{sub 1}/n monoclinic system with chemical formula [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+}(1) and Eu{sup 3+}(2)).The luminescence properties of both compounds were studied. In the compound (1), a broad emission band was observed at 479 nm, redshifted by 70 nm in comparison of the free ligand. In (2), the typical f–f transition was observed with a maximum peak at 618 nm, related with the red emission of the europium ions. Computational methods were performed to simulate the crystal structure of (2). The theoretical calculations of the intensity parameters are in good agreement with the experimental values. - Graphical abstract: Scheme of obtaining the ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) and two new isostructural 3D-coordination polymers [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+} and Eu{sup 3+}) by hydrothermal synthesis. Display Omitted - Highlights: • The ligand 2,5-piperazinedione-1,4-diacetic acid was synthetized using the hydrothermic method and characterized. • Two new 3D-coordination polymers with this ligand containing Gd{sup 3+} and Eu{sup 3+} ions

  4. Ion conductivity and transport by porous coordination polymers and metal-organic frameworks.

    PubMed

    Horike, Satoshi; Umeyama, Daiki; Kitagawa, Susumu

    2013-11-19

    Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have been recognized for their easy design and the dynamic behavior of the ionic components in the structures. These PCP/MOFs consist of metal ions (or clusters) and organic ligands structured via coordination bonds. They could have highly concentrated mobile ions with dynamic behavior, and their characteristics have inspired the design of a new class of ion conductors and transporters. In this Account, we describe the state-of-the-art of studies of ion conductivity by PCP/MOFs and nonporous coordination polymers (CPs) and offer future perspectives. PCP/MOF structures tend to have high hydrophilicity and guest-accessible voids, and scientists have reported many water-mediated proton (H(+)) conductivities. Chemical modification of organic ligands can change the hydrated H(+) conductivity over a wide range. On the other hand, the designable structures also permit water-free (anhydrous) H(+) conductivity. The incorporation of protic guests such as imidazole and 1,2,4-triazole into the microchannels of PCP/MOFs promotes the dynamic motion of guest molecules, resulting in high H(+) conduction without water. Not only the host-guest systems, but the embedding of protic organic groups on CPs also results in inherent H(+) conductivity. We have observed high H(+) conductivities under anhydrous conditions and in the intermediate temperature region of organic and inorganic conductors. The keys to successful construction are highly mobile ionic species and appropriate intervals of ion-hopping sites in the structures. Lithium (Li

  5. Redox-active porous coordination polymer based on trinuclear pivalate: Temperature-dependent crystal rearrangement and redox-behavior

    SciTech Connect

    Lytvynenko, Anton S.; Kiskin, Mikhail A.; Dorofeeva, Victoria N.; Mishura, Andrey M.; Titov, Vladimir E.; Kolotilov, Sergey V.; Eremenko, Igor L.; Novotortsev, Vladimir M.

    2015-03-15

    Linking of trinuclear pivalate Fe{sub 2}NiO(Piv){sub 6} (Piv=O{sub 2}CC(CH{sub 3}){sub 3}) by 2,6-bis(4-pyridyl)-4-(1-naphthyl)pyridine (L) resulted in formation of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)·Solv, which was characterized in two forms: DMSO solvate Fe{sub 2}NiO(Piv){sub 6}(L)(DMSO)·2.5DMSO (1) or water solvate Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) (2). X-ray structure of 1 was determined. Crystal lattice of 1 at 160 K contained open channels, filled by captured solvent, while temperature growth to 296 K led to the crystal lattice rearrangement and formation of closed voids. Redox-behavior of 2 was studied by cyclic voltammetry for a solid compound, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. The presence of pores in desolvated sample Fe{sub 2}NiO(Piv){sub 6}(L) was confirmed by the measurements of N{sub 2} and H{sub 2} adsorption at 77 K. Potential barriers of the different molecules diffusion through pores were estimated by the means of molecular mechanics. - Graphical abstract: Redox-behavior of 1D-porous coordination polymer Fe{sub 2}NiO(Piv){sub 6}(L)(H{sub 2}O) was studied by cyclic voltammetry in thin film, deposited on glassy-carbon electrode. Redox-activity of L preserved upon incorporation in the coordination polymer. Potential barriers of different molecules diffusion through pores were estimated by the means of molecular mechanics. - Highlights: • Porous 1D coordination polymer was synthesized. • Temperature growth led to pores closing due to crystal lattice rearrangement. • Redox-activity of ligand preserved upon incorporation into coordination polymer. • Redox-properties of solid coordination polymer were studied in thin film. • Diffusion barriers were evaluated by molecular mechanics.

  6. Complementary in situ reactivity of isomeric dipyridylamide precursors and its effect on dimensionality of cadmium 5-nitroisophthalate coordination polymers

    NASA Astrophysics Data System (ADS)

    O'Donovan, Megan E.; LaDuca, Robert L.

    2014-07-01

    Hydrothermal treatment of cadmium nitrate, 5-nitroisophthalic acid (H2nip) and one of two isomeric dipyridylamides resulted in coordination polymer crystalline solids that manifested different in situ reactivity and dimensionality, as ascertained by single crystal X-ray diffraction. Hydrolysis of 3-pyridylisonicotinamide (3-pina) afforded the 3-aminopyridine (3-ampyr) ligands observed in the 1-D ladder polymer {[Cd(nip)(3-ampyr)(H2O)]ṡ2H2O}n (1). Conversely, hydrolysis of the isomeric precursor 3-pyridylnicotinamide (3-pna) generated the monoanionic nicotinate ligands in the 2-D coordination polymer [Cd2(nip)(nic)2(H2O)2]n (2). Compound 2 displays {Cd2(OCO)2} eight-membered ring dimeric units linked into (6,3) graphite-type slab motifs. Luminescent properties of these two new materials are also presented.

  7. Bringing an "old" biological buffer to coordination chemistry: new 1D and 3D coordination polymers with [Cu(4)(Hbes)(4)] cores for mild hydrocarboxylation of alkanes.

    PubMed

    Kirillov, Alexander M; Coelho, Jaime A S; Kirillova, Marina V; da Silva, M Fátima C Guedes; Nesterov, Dmytro S; Gruenwald, Katrin R; Haukka, Matti; Pombeiro, Armando J L

    2010-07-19

    New water-soluble 1D and 3D Cu(II)/Na coordination polymers 1-3 bearing unprecedented [Cu(4)(Hbes)(4)] cores have been easily generated by aqueous-medium self-assembly and fully characterized, thus opening up the use of the common biological buffer H(3)bes, (HO(3)SCH(2)CH(2))N(CH(2)CH(2)OH)(2), in synthetic coordination chemistry. Apart from representing the first isolated and structurally characterized coordination compounds derived from H(3)bes, 1-3 show a remarkable promoting effect in the mild aqueous-medium hydrocarboxylation, by CO and H(2)O, of gaseous alkanes (C(3)H(8) and n-C(4)H(10)) to the corresponding carboxylic acids, which are obtained in up to 95% yields based on the alkane.

  8. Molecular structure and magnetic properties of acetato-bridged lanthanide(III) dimers

    SciTech Connect

    Panagiotopoulos, A.; Zafiropoulos, T.F.; Perlepes, S.P.

    1995-09-13

    Structural, magnetic, and EPR studies of diaquatetrakis({mu}-acetato)dicopper(II) have provided important insight into the magnetic interaction phenomenon in polynuclear species involving 3d ions. This compound may be considered at the archetype of the exchange-coupled copper(II) dimers. Until now, no compound of the same nature involving lanthanide(III) ions had been reported, and the factors determining the sign and the magnitude of the magnetic interaction between lanthanide(III) ions are far from being well understood. Herein the authors report on the synthesis, the structure and the magnetic properties of two lanthanide(III) dimers, namely [Ln{sub 2}(CH{sub 3}CO{sub 2}){sub 6-} (phen){sub 2}] with phen = o-phenanthroline and Ln = Ce (1) and Gd (2).

  9. Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers

    PubMed Central

    Wright, James S.; Vitórica-Yrezábal, Iñigo J.; Adams, Harry; Thompson, Stephen P.; Hill, Adrian H.; Brammer, Lee

    2015-01-01

    A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene)n]·m(arene), 1 (arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2], 2a and/or 2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η1,η1 manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations. PMID:25866656

  10. Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers.

    PubMed

    Wright, James S; Vitórica-Yrezábal, Iñigo J; Adams, Harry; Thompson, Stephen P; Hill, Adrian H; Brammer, Lee

    2015-03-01

    A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene) n ]·m(arene), 1 (arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2], 2a and/or 2b , with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b , not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η(1),η(1) manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations. PMID:25866656

  11. Synthesis, crystal structures and characterization of four coordination polymers based on 5-amino-2,4,6-triiodoisophthalic acid

    SciTech Connect

    Zhang Koulin; Chang Yan; Zhang Jingbo; Yuan Limin; Deng Ye; Diao Guowang; Ng, Seik Weng

    2011-05-15

    One homochiral 1D coordination polymer [Cu(ATIBDC)(2,2'-bipy)].3H{sub 2}O.CH{sub 3}OH (1) and three achiral 1D coordination polymers: [Cd(ATIBDC)(2,2'-bipy)(H{sub 2}O)].3H{sub 2}O (2), [Cd(ATIBDC)(phen)(H{sub 2}O)].4H{sub 2}O (3), and [Mn(ATIBDC)(phen){sub 2}].5H{sub 2}O (4) have been synthesized and characterized (H{sub 2}ATIBDC=5-amino-2,4,6-triiodoisophthalic acid, 2,2'-bipy=2,2'-bipyridine, and phen=1,10-phenanthroline). Extended high dimensional network architectures are further constructed with the help of weak secondary interactions, such as hydrogen bonding, aromatic stacking, and halogen bonding (C-I..{pi} and C-I...N/O). Complex 1 crystallizes in the monoclinic system with chiral space group P2(1) and exhibits a right-handed 2{sub 1} helical chain structure. The homochirality of 1 was confirmed by CD spectrum. Interestingly, two new configurations of decameric water cluster are found in 3 and 4. The acyclic tetrameric cluster (H{sub 2}O){sub 3}(CH{sub 3}OH) in 1 and (H{sub 2}O){sub 4} in 2 array into highly ordered helical infinite chains. Thermal stabilities of all the complexes have been studied. Solid state fluorescent properties of the Cd(II) complexes have been explored. -- Graphical abstract: The synthesis, crystal structures and characterization of one 1D homochiral coordination polymer and three achiral 1D coordination polymers with 5-amino-2,4,6-triiodoisophthalic acid (H{sub 2}ATIBDC) are reported. Display Omitted highlights: > Four 1D coordination polymers with 5-amino-2,4,6-triiodoisophthalate are reported. > The halogen bonds play important roles in the supramolecular assembly. > Solid state fluorescent properties of the Cd(II) complexes are explored.

  12. The influence of different coordination environments on one-dimensional Cu(ii) coordination polymers for the photo-degradation of organic dyes.

    PubMed

    Hussain, Navid; Bhardwaj, Vimal K

    2016-05-01

    Three new Cu(ii) coordination polymers, namely, {[Cu3(L(1))(NO3)2(DMF)(H2O)]·3(DMF)}n (), [Cu3(L(1))(Cl)2(DMF)2]n () and [Cu3(L(2))(NO3)4(H2O)4]n (), were synthesized from pyridine-2,6-dicarbohydrazide based imine linked tritopic ligands. All the complexes were characterized using elemental analysis, IR, UV-vis spectroscopy and ESI-MS. The solid state structures of complexes were determined using single crystal X-ray crystallography. The complexes contain trinuclear copper units connected through different anions that lead to the formation of one dimensional (ID) chain structures. Depending upon the anion of the copper salt and donor atoms of the ligands used in complexation, a small variation in the structures was observed. In complex , the trinuclear copper units are connected by phenoxo-bridging (μ2-O(-)) along with one coordinated water molecule, whereas complex is connected through chloride bridging (μ2-Cl) and complex is connected through nitrate ions (μ-[O-N-O]) along with four water molecules. Photo-catalytic activities of the synthesized complexes () were investigated. All the complexes were found to be photo-catalytically active; however, the distinct coordination environment of the metal ions (i.e. difference in the coordinated water molecules and donor sites of ligands) played a significant role in the catalytic activities. Therefore, this study presents comparative photo-catalytic studies of different coordination environments of metal ions in one-dimensional Cu(ii) coordination polymers. The results provide a potential pathway for the rational design of more efficient photo-catalysts. PMID:27054292

  13. Syntheses, structures and luminescence properties of lanthanide coordination polymers with helical character

    SciTech Connect

    Zhou Ruisha; Cui Xiaobing; Song Jiangfeng; Xu Xiaoyu; Xu Jiqing Wang Tiegang

    2008-08-15

    A series of lanthanide coordination polymers, (Him){sub n}[Ln(ip){sub 2}(H{sub 2}O)]{sub n} [Ln=La(1), Pr(2), Nd(3) and Dy(4), H{sub 2}ip=isophthalic acid, im=imidazole] and [Y{sub 2}(ip){sub 3}(H{sub 2}O){sub 2}]{sub n}.nH{sub 2}O (5), have been synthesized and characterized by elemental analyses, infrared (IR), ultraviolet-visible-near infrared (UV-Vis-NIR) and single-crystal X-ray diffraction analyses. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 features a 2-D network making of two different kinds of quadruple-helical chains. Compounds 2 and 3 present the characteristic emissions of Pr(III) and Nd(III) ions in NIR region, respectively. Compound 4 shows sensitized luminescence of Dy(III) ions in visible region. - Graphical abstract: A series of lanthanide coodination polymers, (Him){sub n}[Ln(ip){sub 2}(H{sub 2}O)]{sub n} [Ln=La(1), Pr(2), Nd(3) and Dy(4)] and [Y{sub 2}(ip){sub 3}(H{sub 2}O){sub 2}]{sub n}.nH{sub 2}O (5), have been reported. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 displays a 2-D network making of two kinds of quadruple-helical chains. Display Omitted.

  14. Ultralong Persistent Room Temperature Phosphorescence of Metal Coordination Polymers Exhibiting Reversible pH-Responsive Emission.

    PubMed

    Yang, Yongsheng; Wang, Ke-Zhi; Yan, Dongpeng

    2016-06-22

    Ultra-long-persistent room temperature phosphorescence (RTP) materials have attracted much attention and present various applications in illumination, displays, and the bioimaging field; however, the persistent RTP is generally from the inorganic phosphor materials to date. Herein, we show that the metal coordination polymers (CPs) could be new types of emerging long-lived RTP materials for potential sensor applications. First, two kinds of Cd-based CPs, Cd(m-BDC)(H2O) (1) and Cd(m-BDC)(BIM) (2) (m-BDC = 1,3-benzenedicarboxylic acid; BIM = benzimidazole), were obtained through a hydrothermal process, and the samples were found to exhibit two-dimensional layered structures, which are stabilized by interlayer C-H···π interaction and π···π interaction, respectively. The CPs show unexpected second-time-scale ultra-long-persistent RTP after the removal of UV excitation, and this persistent emission can be detected easily on a time scale of 0-10 s. The CPs also feature a tunable luminescence decay lifetime by adjusting their coordination situation and packing fashion of ligands. Theoretical calculation further indicates that the introduction of the second ligand could highly influence the electronic structure and intermolecular electron transfer toward tailoring the RTP of the CP materials. Moreover, CP 2 exhibits well-defined pH- and temperature-dependent phosphorescence responses. Therefore, this work provides a facile way to develop new type of CPs with steady-state and dynamic tuning of the RTP properties from both experimental and theoretical perspectives, which have potential applications in the areas of displays, pH/temperature sensors, and phosphorescence logic gates. On account of suitable incorporation of inorganic and organic building blocks, it can be expected that the ultra-long-persistent RTP CPs can be extended to other similar systems due to the highly tunable structures and facile synthesis routes. PMID:27253185

  15. Different dimensional coordination polymers with 4,4'-oxybis(benzoate): Syntheses, structures and properties

    SciTech Connect

    Lun, Huijie; Li, Yamin; Zhang, Xudong; Yang, Jing-He; Xiao, Changyu; Xu, Yanqing; Li, Junrui

    2014-07-01

    Five transition-metal coordination polymers, namely, [Zn{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (1), [Cd{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (2), [Zn(oba)(H{sub 2}O)]{sub n} (3), [Ag{sub 2}(oba)]{sub n} (4) and [Co(oba)(H{sub 2}O){sub 2}]{sub n} (5) (H{sub 2}oba=4,4′-oxydibenzoic acid), have been achieved under hydrothermal conditions and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isomorphism, featuring pillared-layer 3D motifs, in which the 2D inorganic layers (Zn{sub 6}Cl{sub 7}){sub n} (or (Cd{sub 6}Cl{sub 7}){sub n}) are connected by oba{sup 2−} pillars. Compound 3 exhibits 1D stair-like chain and extends to a 3D network by two different interchain O–H–O hydrogen bonding interactions while compound 4 features wave chains and stretches to 2D layer by interchain Ag–O weak contacts. Compound 5 shows 2D network in which Co-chains are pillared by oba{sup 2−} ligand and then forms a 3D network by four different O–H–O hydrogen bonding interactions. Furthermore, 1–4 exhibit luminescent properties at a solid state and 5 shows antiferromagnetic behavior. - Graphical abstract: Five new transition-metal coordination complexes 1–5 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses (TGA), photoluminescent spectra and magnetic measurement. - Highlights: • Compound 1 exhibits a pillared-layer 3D network. • The photoluminescent properties of 1–4 have been measured. • Compound 5 exhibits antiferromagnetic behavior.

  16. Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake.

    PubMed

    Leroux, Maxime; Mercier, Nicolas; Allain, Magali; Dul, Marie-Claire; Dittmer, Jens; Kassiba, Abdel Hadi; Bellat, Jean-Pierre; Weber, Guy; Bezverkhyy, Igor

    2016-09-01

    The zwitterionic bipyridinium carboxylate ligand 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium (pc1) in the presence of cadmium chloride affords novel porous coordination polymers (PCPs): [Cd4(pc1)3Cl6]·CdCl4·guest (1) crystallizing in the P3̅1c space group. In the structure, [Cd4Cl6(CO2)6] building units are linked together by six pc1 ligands, leading to a 3D high-symmetrical network exhibiting hexagonal channels along the c axis. The walls of this PCP consist of cationic electron-acceptor bipyridinium units. The PCP 1 reversibly adsorbs H2O and CH3OH up to about 0.1 g/g at saturation showing the adsorption isotherms characteristic of a moderately hydrophilic sorbent. Adsorption of ammonia (NH3) follows a different pattern, reaching an exceptional uptake of 0.39 g/g (22.3 mmol/g) after the first adsorption cycle. Although the crystalline structure of 1 collapses after the first adsorption, the solid can be regenerated and maintains the capacity of 0.29 g/g (17 mmol/g) in the following cycles. We found that the high NH3 uptake is due to a combination of pore filling taking place below 150 h·Pa and chemisorption occurring at higher pressures. The latter process was shown to involve two phenomena: (i) coordination of NH3 molecules to Cd(2+) cations as follows from (113)Cd NMR and (ii) strong donor-acceptor interactions between NH3 molecules and pc1 ligands. PMID:27500980

  17. Fluorescent Sulfur-Tagged Europium(III) Coordination Polymers for Monitoring Reactive Oxygen Species.

    PubMed

    Wang, Huai-Song; Bao, Wen-Jing; Ren, Shi-Bin; Chen, Ming; Wang, Kang; Xia, Xing-Hua

    2015-07-01

    Oxidative stress caused by reactive oxygen species (ROS) is harmful to biological systems and implicated in various diseases. A variety of selective fluorescent probes have been developed for detecting ROS to uncover their biological functions. Generally, the preparation of the fluorescent probes usually undergoes multiple synthetic steps, and the successful fluorescent sensing usually relies on trial-and-error tests. Herein we present a simple way to prepare fluorescent ROS probes that can be used both in biological and environmental systems. The fluorescent europium(III) coordination polymers (CPs) are prepared by simply mixing the precursors [2,2'-thiodiacetic acid and Eu(NO3)3·6H2O] in ethanol. Interestingly, with the increase of reaction temperature, the product undergoes a morphological transformation from microcrystal to nanoparticle while the structure and fluorescent properties retain. The fluorescence of the sulfur-tagged europium(III) CPs can be selectively quenched by ROS, and thus, sensitive and selective monitoring of ROS in aerosols by the microcrystals and in live cells by the nanoparticles has been achieved. The results reveal that the sulfur-tagged europium(III) CPs provide a novel sensor for imaging ROS in biological and environmental systems.

  18. Synthesis, structures, and luminescent properties of uranyl terpyridine aromatic carboxylate coordination polymers.

    PubMed

    Thangavelu, Sonia G; Andrews, Michael B; Pope, Simon J A; Cahill, Christopher L

    2013-02-18

    Six novel uranyl terpyridine aromatic carboxylate coordination polymers, [UO(2)(C(6)H(2)O(4)S)(C(15)H(11)N(3))] (1), [UO(2)(C(6)H(2)O(4)S)(C(15)H(10)N(3)Cl)]·H(2)O (2), [UO(2)(C(8)H(4)O(4))(C(15)H(11)N(3))] (3), [UO(2)(C(8)H(4)O(4))(C(15)H(10)N(3)Cl)] (4), [UO(2)(C(12)H(6)O(4))(C(15)H(11)N(3))] (5), and [UO(2)(C(12)H(6)O(4))(C(15)H(10)N(3)Cl)] (6), were synthesized under solvothermal conditions and characterized by single-crystal and powder X-ray diffraction and luminescence and UV-vis spectroscopy. Compounds 1, 2, and 5 crystallize as molecular uranyl dimers, whereas compounds 3, 4, and 6 contain ladder motifs of uranyl centers. Fluorescence spectra of 1-4 show characteristic UO(2)(2+) emission, wherein bathochromic and hypsochromic shifts are noted as a function of organic species. In contrast, uranyl emission from 5 and 6 is quenched by the naphthalene dicarboxylic acid linker molecules.

  19. Self-assembled nanoscale coordination polymers with trigger release properties for effective anticancer therapy

    NASA Astrophysics Data System (ADS)

    Liu, Demin; Poon, Christopher; Lu, Kuangda; He, Chunbai; Lin, Wenbin

    2014-06-01

    Nanoscale coordination polymers (NCPs) are self-assembled from metal ions and organic bridging ligands, and can overcome many drawbacks of existing drug delivery systems by virtue of tunable compositions, sizes and shapes, high drug loadings, ease of surface modification and intrinsic biodegradability. Here we report the self-assembly of zinc bisphosphonate NCPs that carry 48±3 wt% cisplatin prodrug and 45±5 wt% oxaliplatin prodrug. In vivo pharmacokinetic studies in mice show minimal uptake of pegylated NCPs by the mononuclear phagocyte system and excellent blood circulation half-lives of 16.4±2.9 and 12.0±3.9 h for the NCPs carrying cisplatin and oxaliplatin, respectively. In all tumour xenograft models evaluated, including CT26 colon cancer, H460 lung cancer and AsPC-1 pancreatic cancer, pegylated NCPs show superior potency and efficacy compared with free drugs. As the first example of using NCPs as nanotherapeutics with enhanced antitumour activities, this study establishes NCPs as a promising drug delivery platform for cancer therapy.

  20. Hydrothermal Synthesis, Crystal Structure and Electrochemical Behavior of 2d Hybrid Coordination Polymer

    NASA Astrophysics Data System (ADS)

    Fan, Weiqiang; Zhu, Lin; Shi, Weidong; Chen, Fuxiao; Bai, Hongye; Song, Shuyan; Yan, Yongsheng

    2013-06-01

    A novel metal-organic coordination polymer [Cu(phen)(L)0.5(H2O)]n (H4L = (N,N‧-5,5‧-bis(isophthalic acid)-p-xylylenediamine, and phen = 1,10-phenanthroline) has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, and single-crystal X-ray diffraction. The crystallographic data show that the title compound crystallizes in monoclinic space group P21/n with a = 10.682(2), b = 15.682(3), c = 11.909(2) Å, β = 91.39(3)°, V = 1994.3(7) Å3, C24H17CuN3O5, Mr = 490.95, Dc = 1.635 g/cm3, F(000) = 1004, Z = 4, μ(MoKα) = 1.141 mm-1, the final R = 0.0418 and wR = 0.0983 for 3578 observed reflections (I > 2σ(I)). The structural analyses reveal that the title compound exhibits shows a 2D layer structure, which are further linked by hydrogen bonding interactions to form a three-dimensional supramolecular network. In addition, the thermal stability and electrochemical behavior of title compound has been studied. CCDC: 900413.

  1. Porous coordination polymers as novel sorption materials for heat transformation processes.

    PubMed

    Janiak, Christoph; Henninger, Stefan K

    2013-01-01

    Porous coordination polymers (PCPs)/metal-organic frameworks (MOFs) are inorganic-organic hybrid materials with a permanent three-dimensional porous metal-ligand network. PCPs or MOFs are inorganic-organic analogs of zeolites in terms of porosity and reversible guest exchange properties. Microporous water-stable PCPs with high water uptake capacity are gaining attention for low temperature heat transformation applications in thermally driven adsorption chillers (TDCs) or adsorption heat pumps (AHPs). TDCs or AHPs are an alternative to traditional air conditioners or heat pumps operating on electricity or fossil fuels. By using solar or waste heat as the operating energy TDCs or AHPs can significantly help to minimize primary energy consumption and greenhouse gas emissions generated by industrial or domestic heating and cooling processes. TDCs and AHPs are based on the evaporation and consecutive adsorption of coolant liquids, preferably water, under specific conditions. The process is driven and controlled by the microporosity and hydrophilicity of the employed sorption material. Here we summarize the current investigations, developments and possibilities of PCPs/MOFs for use in low-temperature heat transformation applications as alternative materials for the traditional inorganic porous substances like silica gel, aluminophosphates or zeolites.

  2. In Vitro Antihepatoma Activity of Novel 3D-Copper Cyanide Supramolecular Coordination Polymers.

    PubMed

    Darwish, Noura M; Sultan, Ahmed S; Malki, Ahmed M; Khamis, Hossam; El-Ziady, Mohamed

    2016-09-01

    This study aimed to investigate the inhibitory effect of novel 3D-organocopper supramolecular coordination polymers (SCPs) on the invasive potential of HepG2 cells. Chemoprevention could represent an important means to inhibit the process of hepatocarcinogenesis. The inhibitory effect of an SCP compound on the proliferation of HepG2 hepatoma cells was evaluated by cell vibility assay. DNA ladder bands were observed by DNA agarose gel electrophoresis. The influence of the SCP compound on phosphorylated ERK1/2, Bcl-2, and β-catenin protein expression of HepG2 cells was analyzed by Western blot. The SCP compound exerted an inhibitory effect on HepG2 cell proliferation in a dose-dependent manner. This inhibitory effect was confirmed by examination of cell morphology and DNA fragmentation. Furthermore, Western blot analysis revealed that phosphorylated ERK1/2 and β-catenin protein expression was inhibited after 24 h of treatment with the SCP compound, and that this event was associated with decreased Bcl-2 expression. We concluded that SCP can effectively inhibit the invasive potential of the ERK signaling pathway in HepG2 cells by altering apoptosis and by inhibiting Bcl-2 and β-catenin, which may play a significant role in this process.

  3. Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand

    PubMed Central

    Noro, Shin-ichiro; Mizutani, Junya; Hijikata, Yuh; Matsuda, Ryotaro; Sato, Hiroshi; Kitagawa, Susumu; Sugimoto, Kunihisa; Inubushi, Yasutaka; Kubo, Kazuya; Nakamura, Takayoshi

    2015-01-01

    The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs. PMID:25592677

  4. One- and two-dimensional Cd(II) coordination polymers incorporating organophosphinate ligands.

    PubMed

    Rood, Jeffrey A; Boyer, Steven; Oliver, Allen G

    2014-11-01

    Reaction of cadmium nitrate with diphenylphosphinic acid in dimethylformamide solvent yielded the one-dimensional coordination polymer catena-poly[[bis(dimethylformamide-κO)cadmium(II)]-bis(μ-diphenylphosphinato-κ(2)O:O')], [Cd(C12H10O2P)2(C3H7NO)2]n, (I). Addition of 4,4'-bipyridine to the synthesis afforded a two-dimensional extended structure, poly[[(μ-4,4'-bipyridine-κ(2)N:N')bis(μ-diphenylphosphinato-κ(2)O:O')cadmium(II)] dimethylformamide monosolvate], {[Cd(C12H10O2P)2(C10H8N2)]·C3H7NO}n, (II). In (II), the 4,4'-bipyridine molecules link the Cd(II) centers in the crystallographic a direction, while the phosphinate ligands link the Cd(II) centers in the crystallographic b direction to complete a two-dimensional sheet structure. Consideration of additional π-π interactions of the phenyl rings in (II) produces a three-dimensional structure with channels that encapsulate dimethylformamide molecules as solvent of crystallization. Both compounds were characterized by single-crystal X-ray diffraction and FT-IR analysis.

  5. Porous coordination polymers as novel sorption materials for heat transformation processes.

    PubMed

    Janiak, Christoph; Henninger, Stefan K

    2013-01-01

    Porous coordination polymers (PCPs)/metal-organic frameworks (MOFs) are inorganic-organic hybrid materials with a permanent three-dimensional porous metal-ligand network. PCPs or MOFs are inorganic-organic analogs of zeolites in terms of porosity and reversible guest exchange properties. Microporous water-stable PCPs with high water uptake capacity are gaining attention for low temperature heat transformation applications in thermally driven adsorption chillers (TDCs) or adsorption heat pumps (AHPs). TDCs or AHPs are an alternative to traditional air conditioners or heat pumps operating on electricity or fossil fuels. By using solar or waste heat as the operating energy TDCs or AHPs can significantly help to minimize primary energy consumption and greenhouse gas emissions generated by industrial or domestic heating and cooling processes. TDCs and AHPs are based on the evaporation and consecutive adsorption of coolant liquids, preferably water, under specific conditions. The process is driven and controlled by the microporosity and hydrophilicity of the employed sorption material. Here we summarize the current investigations, developments and possibilities of PCPs/MOFs for use in low-temperature heat transformation applications as alternative materials for the traditional inorganic porous substances like silica gel, aluminophosphates or zeolites. PMID:23945102

  6. Spectroscopic properties and the catalytic activity of new organo-lead supramolecular coordination polymer containing quinoxaline

    NASA Astrophysics Data System (ADS)

    Etaiw, Safaa El-din H.; Abdou, Safaa N.

    2015-01-01

    The 3D-supramolecular coordination polymer (SCP) 3∞[ Cu2(CN)3(Me3Pb)(qox)], 1, as the first example of the CuCN SCP containing the (Me3Pb) fragment, was explored to investigate its catalytic and photo-catalytic activities. The structure of 1 contains two chemically identical but crystallographically different [Cu2(CN)3ṡMe3Pbṡqox]2 units with four Cu(I) sites assuming distorted TP-3 geometry. Two non-linear chains of equal abundance are formed producing corrugated parallel chains which are connected laterally by quinoxaline creating 2D-layers which are arranged parallel in an (AB⋯AB⋯AB)n fashion forming 3D-network. IR, mass, electronic absorption and fluorescence spectra are also investigated. The SCP 1 is diamagnetic and exhibits good catalytic and photo-catalytic activities for the degradation of methylene blue (MB). The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. The efficiency of recycled the 1 and the mechanism of degradation of MB dye were investigated.

  7. Spectroscopic properties and the catalytic activity of new organo-lead supramolecular coordination polymer containing quinoxaline.

    PubMed

    Etaiw, Safaa El-din H; Abdou, Safaa N

    2015-01-25

    The 3D-supramolecular coordination polymer (SCP) (3)∞[ Cu2(CN)3(Me3Pb)(qox)], 1, as the first example of the CuCN SCP containing the (Me3Pb) fragment, was explored to investigate its catalytic and photo-catalytic activities. The structure of 1 contains two chemically identical but crystallographically different [Cu2(CN)3⋅Me3Pb⋅qox]2 units with four Cu(I) sites assuming distorted TP-3 geometry. Two non-linear chains of equal abundance are formed producing corrugated parallel chains which are connected laterally by quinoxaline creating 2D-layers which are arranged parallel in an (AB⋯AB⋯AB)n fashion forming 3D-network. IR, mass, electronic absorption and fluorescence spectra are also investigated. The SCP 1 is diamagnetic and exhibits good catalytic and photo-catalytic activities for the degradation of methylene blue (MB). The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. The efficiency of recycled the 1 and the mechanism of degradation of MB dye were investigated.

  8. Two coordination polymers of manganese(II) isophthalate and their preparation, structures, and magnetic properties

    SciTech Connect

    Chen Jinxi; Wang Jingjing; Ohba, Masaaki

    2012-01-15

    Two manganese coordination polymers, [Mn{sub 2}(ip){sub 2}(dmf)]{center_dot}dmf (1) and [Mn{sub 4}(ip){sub 4}(dmf){sub 6}]{center_dot}2dmf (2) (ip=isophthalate; dmf=N,N-dimethylformamide), have been synthesized and characterized. X-ray crystal structural data reveal that compound 1 crystallizes in triclinic space group P-1, a=9.716(3) A, b=12.193(3) A, c=12.576(3) A, {alpha}=62.19(2) Degree-Sign , {beta}=66.423(17) Degree-Sign , {gamma}=72.72(2) Degree-Sign , Z=2, while compound 2 crystallizes in monoclinic space group Cc, a=19.80(3) A, b=20.20(2) A, c=18.01(3) A, {beta}=108.40(4) Degree-Sign , Z=4. Variable-temperature magnetic susceptibilities of compounds 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions. - Graphical abstract: Three-dimensional porous and two-dimensional layered manganese isophthalates have been prepared. Magnetic susceptibility measurements exhibit overall weak antiferromagnetic interactions between the Mn(II) ions in both compounds. Highlights: Black-Right-Pointing-Pointer Two manganese isophthalates have been prepared. Black-Right-Pointing-Pointer Compound 1 adopts a three-dimensional porous structure. Black-Right-Pointing-Pointer Compound 2 adopts a two-dimensional layered structure. Black-Right-Pointing-Pointer Magnetic properties of both compounds are investigated.

  9. Synthesis and characterization of the mixed ligand coordination polymer CPO-5

    NASA Astrophysics Data System (ADS)

    Kongshaug, Kjell Ove; Fjellvåg, Helmer

    2003-11-01

    The synthesis and crystal structures of a novel coordination polymer and its high-temperature variant are described. The as-synthesized material (CPO-5-as), of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate)·3H 2O, crystallizes in the triclinic space group P-1 (No. 2) with a=11.0197(2), b=14.2975(3), c=7.6586(1) Å, α=95.9760(9)°, β=108.026(1)°, γ=91.373(1)° and V=1139.16(4) Å 3. CPO-5-as is composed of tetrahedral zinc centers that are connected by the organic linkers to give five independent, interpenetrating diamond networks. In the structure, there is additional space for channels that are filled with three water molecules. These water molecules can be removed, leading to an anhydrous variant at 130 oC. CPO-5-130, of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate), crystallizes in the triclinic space group P-1 (No. 2) with a=11.1844(6), b=14.0497(7), c=7.7198(3) Å, α=96.917(2)°, β=109.527(2)°, γ=89.115(3)° and V=1134.6(1) Å 3. The structure of the five interpenetrating networks is virtually unchanged after the dehydration resulting in CPO-5-130 being a porous structure with an estimated free volume of 19.8%.

  10. Preparation of nanocrystalline metal oxides and intermetallic phases by controlled thermolysis of organometallic coordination polymers

    NASA Astrophysics Data System (ADS)

    Rehbein, Marcus; Epple, Matthias; Fischer, R. Dieter

    2000-06-01

    Organometallic coordination polymers of the super-Prussian blue type [(Me 3Sn) nM(CN) 6] (Me=CH 3; n=3, 4; M=Fe, Co, Ru) were subjected to thermolysis in different atmospheres (air, argon, hydrogen/nitrogen). In air, oxides were found: Fe 2O 3/SnO 2 (crystalline and nanocrystalline), Co 2SnO 4 and RuO 2. In argon and in hydrogen, the intermetallic phases FeSn 2, CoSn 2, Ru 3Sn 7 and Fe 3SnC were obtained. A detailed mechanistic study was carried out using thermogravimetry (TG), X-ray diffraction (XRD), X-ray absorption spectroscopy (EXAFS) at Fe, Co, Ru and Sn K-edges, infrared spectroscopy (IR) and elemental analysis. Below 250°C, Me 3SnCN and (CN) 2 are released, whereas above 250°C oxidation or pyrolysis leads to the corresponding oxides or intermetallic phases. Polymeric cyanides containing at least two metals have turned out to be suitable precursors to prepare well-defined oxides and intermetallic phases at comparatively low temperature.

  11. Spectroscopic properties and the catalytic activity of new organo-lead supramolecular coordination polymer containing quinoxaline.

    PubMed

    Etaiw, Safaa El-din H; Abdou, Safaa N

    2015-01-25

    The 3D-supramolecular coordination polymer (SCP) (3)∞[ Cu2(CN)3(Me3Pb)(qox)], 1, as the first example of the CuCN SCP containing the (Me3Pb) fragment, was explored to investigate its catalytic and photo-catalytic activities. The structure of 1 contains two chemically identical but crystallographically different [Cu2(CN)3⋅Me3Pb⋅qox]2 units with four Cu(I) sites assuming distorted TP-3 geometry. Two non-linear chains of equal abundance are formed producing corrugated parallel chains which are connected laterally by quinoxaline creating 2D-layers which are arranged parallel in an (AB⋯AB⋯AB)n fashion forming 3D-network. IR, mass, electronic absorption and fluorescence spectra are also investigated. The SCP 1 is diamagnetic and exhibits good catalytic and photo-catalytic activities for the degradation of methylene blue (MB). The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. The efficiency of recycled the 1 and the mechanism of degradation of MB dye were investigated. PMID:25124847

  12. Synthesis and crystal structures of two nickel coordination polymers generated from asymmetric malate ligand

    SciTech Connect

    Guo Yaqin; Xiao Dongrong; Wang Enbo . E-mail: wangenbo@public.cc.jl.cn; Lu Ying; Lue Jian; Xu Xinxin; Xu Lin

    2005-03-15

    Two nickel coordination polymers [Ni(H{sub 2}O)(C{sub 4}H{sub 4}O{sub 5})].H{sub 2}O 1 and [Ni(H{sub 2}O)(mal)(phen)] 2, have been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Crystal data for 1: C{sub 4}H{sub 8}O{sub 7}Ni, monoclinic Cc, a=13.156(3)A, b=7.5436(15)A, c=9.6982(19)A, {beta}=130.96(3){sup o}, Z=4. Crystal data for 2: C{sub 16}H{sub 14}N{sub 2}O{sub 6}Ni, orthorhombic Pna2{sub 1}, a=9.6113(19)A, b=19.691(4)A, c=8.0944(16)A, Z=4. Compound 1 is constructed from [Ni(H{sub 2}O)(C{sub 4}H{sub 4}O{sub 5})] sheets pillared through {beta}-carboxylate groups into a 3D framework, which exhibits a diamond-like network. Compound 2 exhibits a 3D supramolecular network. To our knowledge, compound 1 represents the first diamond-like topology in the system of metal-malate. Other characterizations by elemental analysis, IR and TG are also described. The magnetic behavior of compound 1 has been studied.

  13. Dual-Emission Luminescence of Magnesium Coordination Polymers Based on Mixed Organic Ligands.

    PubMed

    Wu, Zhao-Feng; Tan, Bin; Deng, Zhong-Hua; Xie, Zai-Lai; Fu, Jing-Jing; Shen, Nan-Nan; Huang, Xiao-Ying

    2016-01-22

    Presented herein are two luminescent magnesium coordination polymers (Mg-CPs), namely [Mg2 (H2O)2 (2-NDC)4 (1,10-phen)2] (1) and [Mg2 (H2O)(1,4-NDC)2 (1,10-phen)] (2), in which 2-NDCH=2-naphthalenecarboxylic acid, 1,4-NDCH2 =1,4-naphthalene dicarboxylic acid, and 1,10-phen=1,10-phenanthroline. Based on the mixed ligands, the title compounds exhibit linker-based photoluminescence (PL) properties thanks to the unique configuration of the Mg(2+) ions. The two compounds show interesting dual emission on excitation of the different luminophores of the mixed linkers. In particular, the emissions of compound 2 could be tuned from green to yellow simply by varying the excitation energies. Furthermore, 2 could be excited by using a commercial λ=450 nm blue LED chip to generate white-light emission, which allows the fabrication of a white-light-emitting diode (WLED) with 20 lm W(-1) luminous efficacy. This work may provide a new method for designing tunable PL CPs by using the low-cost and abundant magnesium ion. PMID:26661529

  14. Surfactant-Assisted Nanocrystalline Zinc Coordination Polymers: Controlled Particle Sizes and Synergistic Effects in Catalysis.

    PubMed

    Huang, Chao; Wang, Huarui; Wang, Xiaolu; Gao, Kuan; Wu, Jie; Hou, Hongwei; Fan, Yaoting

    2016-04-25

    Different morphologies and particle sizes of two crystalline zinc-based coordination polymers (CPs), [Zn(pytz)H2 O]n (1; H2 pytz=2,6-bis(tetrazole)pyridine) and [Zn2 (pytz)2 4 H2 O] (2), from the bulk scale to the nanoscale, could be obtained under solvothermal conditions with different surfactants (polyvinylpyrrolidone (PVP) or polyethylene glycol (PEG) 2000) as templates. PVP and PEG 2000 could act as capping and structure-directing agents, respectively, to influence the growth of crystalline particles and control their sizes. CP 1 exhibits a two-dimensional framework with window-like units and 2 shows a bimetallic structure. Nanocrystalline 1 and 2 were used as heterogeneous catalysts to study how adjacent catalytic active sites synergistically effected their catalytic reactivities in the direct catalytic conversion of aromatic dinitriles into oxazolines. The results showed that 1 produced bis-oxazolines as the sole products, whereas 2 gave the mono-oxazolines as the major products under the same reaction conditions. PMID:26997347

  15. Uniform Cerium-Based Coordination Polymer Microsnheres: Preoaration and Upconversion Emission.

    PubMed

    Nie, Zhi-Wen; Zeng, Cheng-Hui; Xie, Gang; Zhong, Sheng-Liang

    2016-04-01

    Homogeneously doped Yb3+ and Er3+ cerium-based coordination polymer (CP) microspheres have been successfully synthesized on a large scale through a simple solvothermal route with 2,5-pyridinedicarboxylic acid (2,5-H2PDC) as the organic linker. CeO2: Yb3+, Er3+ porous microspheres were obtained by annealing the corresponding CP microspheres at 600 °C for 4 h under atmospheric pressure. These as-prepared products were characterized by Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), energy-dispersion X-ray (EDX) spectroscopy, Thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis. The room temperature upconversion luminescent spectra of the as-prepared microspheres were carried out by 980 nm NIR light excitation. Interestingly, Yb3+ and Er3+ codoped CP microspheres give a single-band emission centered at 673 nm, while the CeO2: Yb3+, Er3+ microspheres give emission in green and red region, with red being the dominant emission. The emission intensity of the CeO2: Yb3+, Er3+ microspheres were much stronger than that of the Yb3+ and Er3+ codoped CP microspheres. PMID:27451693

  16. Molecular magnets based on homometallic hexanuclear lanthanide(III) complexes.

    PubMed

    Das, Sourav; Hossain, Sakiat; Dey, Atanu; Biswas, Sourav; Sutter, Jean-Pascal; Chandrasekhar, Vadapalli

    2014-05-19

    The reaction of lanthanide(III) chloride salts (Gd(III), Dy(III), Tb(III), and Ho(III)) with the hetero donor chelating ligand N'-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl)picolinohydrazide (LH3) in the presence of triethylamine afforded the hexanuclear Ln(III) complexes [{Ln6(L)2(LH)2}(μ3-OH)4][MeOH]p[H2O]q[Cl]4·xH2O·yCH3OH (1, Ln = Gd(III), p = 4, q = 4, x = 8, y = 2; 2, Ln = Dy(III), p = 2, q = 6, x = 8, y = 4; 3, Ln = Tb(III), p = 2, q = 6, x = 10, y = 4; 4, Ln = Ho(III), p = 2, q = 6, x = 10, y = 2). X-ray diffraction studies revealed that these compounds possess a hexanuclear [Ln6(OH)4](14+) core consisting of four fused [Ln3(OH)](8+) subunits. Both static (dc) and dynamic (ac) magnetic properties of 1-4 have been studied. Single-molecule magnetic behavior has been observed in compound 2 with an effective energy barrier and relaxation time pre-exponential parameters of Δ/kB = 46.2 K and τ0 = 2.85 × 10(-7) s, respectively. PMID:24766539

  17. Luminescent chiral lanthanide(III) complexes as potential molecular probes

    PubMed Central

    Muller, Gilles

    2009-01-01

    This perspective gives an introduction into the design of luminescent lanthanide(III)-containing complexes possessing chiral properties and used to probe biological materials. The first part briefly describes general principles, focusing on the optical aspect (i.e. lanthanide luminescence, sensitization processes) of the most emissive trivalent lanthanide ions, europium and terbium, incorporated into molecular luminescent edifices. This is followed by a short discussion on the importance of chirality in the biological and pharmaceutical fields. The second part is devoted to the assessment of the chiroptical spectroscopic tools available (typically circular dichroism and circularly polarized luminescence) and the strategies used to introduce a chiral feature into luminescent lanthanide(III) complexes (chiral structure resulting from a chiral arrangement of the ligand molecules surrounding the luminescent center or presence of chiral centers in the ligand molecules). Finally, the last part illustrates these fundamental principles with recent selected examples of such chiral luminescent lanthanide-based compounds used as potential probes of biomolecular substrates. PMID:19885510

  18. Honeycomb-shaped coordination polymers based on the self-assembly of long flexible ligands and alkaline-earth ions

    NASA Astrophysics Data System (ADS)

    Lian, Chen; Liu, Liu; Guo, Xu; Long, Yinshuang; Jia, Shanshan; Li, Huanhuan; Yang, Lirong

    2016-01-01

    Two novel coordination polymers, namely, [Ca(NCP)2]∞ (I) and [Sr(NCP)2]∞ (II) were synthesized under hydrothermal conditions based on 2-(4-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (HNCP) and characterized by elemental analysis, infrared spectrometry, X-ray powder diffraction and single crystal X-ray diffraction. Findings indicate that I and II are isomorphous and isostructural, containing the unit of M(NCP-)4 (M=Ca(II) and Sr(II)), based on which to assemble into three-dimensional (3D) porous 4-fold interpenetration honeycomb-shaped neutral coordination polymers (CPs). Between the adjacent lamellar structures in I and II, there exist π-π interactions between the pyridine rings belonging to phenanthroline of NCP- which stabilize the frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability.

  19. One- and two-dimensional divalent copper coordination polymers based on kinked organodiimine and long flexible aliphatic dicarboxylate ligands

    NASA Astrophysics Data System (ADS)

    Mallika Krishnan, Subhashree; Supkowski, Ronald M.; LaDuca, Robert L.

    2008-11-01

    Hydrothermal synthesis under acidic conditions has afforded a pair of divalent copper coordination polymers containing the kinked dipodal tethering organodiimine 4,4'-dipyridylamine (dpa) and flexible long-chain aliphatic dicarboxylate ligands. The new materials were characterized by single crystal X-ray structure determination, infrared spectroscopy, and thermogravimetric analysis. [CuCl(suberate) 0.5(dpa)] ( 1) manifests 1-D ladder-like motifs aggregated into 3-D through hydrogen bonding and copper-mediated supramolecular interactions. Extension of the aliphatic chain within the dicarboxylate ligand by one methylene unit resulted in {[Cu(azelate)(dpa)(H 2O)] · 3H 2O} ( 2), a (4,4) rhomboid grid 2-D coordination polymer encapsulating acyclic water molecule trimers.

  20. Recovery of metals from simulant spent lithium-ion battery as organophosphonate coordination polymers in aqueous media.

    PubMed

    Perez, Emilie; Andre, Marie-Laure; Navarro Amador, Ricardo; Hyvrard, François; Borrini, Julien; Carboni, Michaël; Meyer, Daniel

    2016-11-01

    An innovative approach is proposed for the recycling of metals from a simulant lithium-ion battery (LIBs) waste aqueous solution. Phosphonate organic linkers are introduced as precipitating agents to selectively react with the metals to form coordination polymers from an aqueous solution containing Ni, Mn and Co in a hydrothermal process. The supernatant is analyzed by ICP-AES to quantify the efficiency and the selectivity of the precipitation and the materials are characterized by Scanning Electron Microscopy (SEM), Powder X-Ray Diffraction (PXRD), Thermogravimetric Analyses (TGA) and nitrogen gas sorption (BET). Conditions have been achieved to selectively precipitate Manganese or Manganese/Cobalt from this solution with a high efficiency. This work describes a novel method to obtain potentially valuable coordination polymers from a waste metal solution that can be generalized on any waste solution. PMID:27362538

  1. Recovery of metals from simulant spent lithium-ion battery as organophosphonate coordination polymers in aqueous media.

    PubMed

    Perez, Emilie; Andre, Marie-Laure; Navarro Amador, Ricardo; Hyvrard, François; Borrini, Julien; Carboni, Michaël; Meyer, Daniel

    2016-11-01

    An innovative approach is proposed for the recycling of metals from a simulant lithium-ion battery (LIBs) waste aqueous solution. Phosphonate organic linkers are introduced as precipitating agents to selectively react with the metals to form coordination polymers from an aqueous solution containing Ni, Mn and Co in a hydrothermal process. The supernatant is analyzed by ICP-AES to quantify the efficiency and the selectivity of the precipitation and the materials are characterized by Scanning Electron Microscopy (SEM), Powder X-Ray Diffraction (PXRD), Thermogravimetric Analyses (TGA) and nitrogen gas sorption (BET). Conditions have been achieved to selectively precipitate Manganese or Manganese/Cobalt from this solution with a high efficiency. This work describes a novel method to obtain potentially valuable coordination polymers from a waste metal solution that can be generalized on any waste solution.

  2. Tube-type coordination polymers: two- and four-silver(I)-mediated linear networking of calix[4]arene tetracarboxylates.

    PubMed

    Park, Ki-Min; Lee, Eunji; Park, Chul Soon; Lee, Shim Sung

    2011-12-01

    Two calix[4]arene tetracarboxylates, [calix[4]arene tetraacetate (K(4)CTA) and calix[4]arene tetrabenzoate (K(4)CTB)] as their potassium salts, have been prepared. Employing these as precursors, two Ag(I) coordination polymers incorporating calix[4]arene units have been successfully prepared and their X-ray crystal structures have been determined. In these, the CTA and CTB derivatives are linearly bound to two and four silver atoms, respectively, to generate unusual tubular nanostructures. A comparative NMR study was undertaken to investigate the nature of the metal ion blocking of the tube as observed in the CTA-derived structure. The thermal properties for both coordination polymers were also examined.

  3. Ultrasonic-assisted synthesis and structural characterization of two new nano-structured Hg(II) coordination polymers.

    PubMed

    Ghasempour, Hosein; Azhdari Tehrani, Alireza; Morsali, Ali

    2015-11-01

    Two new Hg(II) coordination polymers containing N,N'-Bis-pyridin-3-ylmethylene-naphtalene-1,5-diamine ligand were synthesized by conventional and sonochemical methods, characterized by spectroscopic techniques (FT-IR and elemental analysis), and their X-ray crystallographic structures were determined. The crystal packing and supramolecular features of these coordination polymers were studied using geometrical analysis and Hirshfeld surface analysis. The crystal structure analysis revealed that H⋯H contacts, C-H⋯π and C-H⋯X (X = Cl for 1 and X = Br for 2) hydrogen bonding interactions are strong enough to govern the supramolecular architecture. The BFDH analysis helps us to compare the predicted morphology to that obtained under ultrasonication. This study may provide further insight into discovering the role of weak intermolecular interactions in the context of nano-supramolecular assembly.

  4. Crystal structures and luminescent properties of lanthanide nitrate coordination polymers with structurally related amide type bridging podands

    SciTech Connect

    Wang, Qing; Yan, Xuhuan; Zhang, Hongrui; Liu, Weisheng; Tang, Yu; Tan, Minyu

    2011-01-15

    A one-dimensional linear chain coordination polymer [ErL{sup I}(NO{sub 3}){sub 3}(CH{sub 3}CO{sub 2}Et)]{sub n} (L{sup I}=1,2-bis{l_brace}[(2'-furfurylaminoformyl)phenoxyl]methyl{r_brace}benzene) and a one-dimensional zig-zag coordination polymer {l_brace}[TbL{sup II}(NO{sub 3}){sub 3}(H{sub 2}O)].(H{sub 2}O){r_brace}{sub n} (L{sup II}=1,2-bis{l_brace}[2'-(2-pyridylmethylaminoformyl)phenoxyl]methyl{r_brace}benzene) were assembled by two structurally related bridging podands L{sup I} and L{sup II} which have uniform skeleton and different terminal groups. In {l_brace}[TbL{sup II}(NO{sub 3}){sub 3}(H{sub 2}O)].(H{sub 2}O){r_brace}{sub n}, the neutral chains were linked by the hydrogen bonding interactions between the free and coordinated water molecules from two different directions to interpenetrate into a 3D supramolecular structure. At the same time, the luminescent properties of the solid Tb(III) nitrate complexes of these podands were investigated at room temperature. The lowest triplet state energy levels T{sub 1} of the podands L{sup I} and L{sup II} indicate that the triplet state energy levels of the antennae are both above the lowest excited resonance level of {sup 5}D{sub 4} of Tb{sup 3+} ion. Thus the absorbed energy could be transferred from ligands to the central Tb{sup 3+} ions. And the influence of the hydrogen bonding on the luminescence efficiencies of the coordination polymers was also discussed. -- Graphical Abstract: Two one-dimensional lanthanide coordination polymers were assembled by two structurally related bridging podands, and the effects of the structures on luminescent properties of the solid Tb(III) nitrate complexes were investigated. Display Omitted Research highlights: > Two structurally related amide type bridging ligands were designed and synthesized. > Two one dimensional lanthanide nitrate coordination polymers were obtained. > The structure effects on luminescent properties of the terbium complexes were discussed.

  5. Anion-controlled assembly of silver-di(aminophenyl)sulfone coordination polymers: Syntheses, crystal structures, and solid state luminescence

    SciTech Connect

    Zhang, Qi-Long; Hu, Peng; Zhao, Yi; Feng, Guang-Wei; Zhang, Yun-Qian; Zhu, Bi-Xue; Tao, Zhu

    2014-02-15

    Five silver coordination polymers, namely, ([Ag(3,3′-daps){sub 2}]·BF{sub 4}){sub n} (1), ([Ag(3,3′-daps){sub 2}]·NO{sub 3}){sub n} (2), [Ag(3,3′-daps)(CF{sub 3}SO{sub 3})]{sub n} (3), ([Ag(4,4′-daps)]·CF{sub 3}SO{sub 3}){sub n} (4), and ([Ag(4,4′-daps)]·ClO{sub 4}){sub n} (5) (3,3′-daps=di(3′-aminodiphenyl)sulfone, and 4,4′-daps=di(4′-aminodiphenyl)sulfone) have been synthesized and structural characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analyses. Complex 1 displays a 1D ladder-like chain with four-connected Ag ions and bridged 3,3′-daps. Complex 2 shows other 1D ladder chain modified by tentacles. Complex 3 is a 2D layer structure with both Ag ions and 3,3′-daps are 3-connected nodes. Complex 4 is another 1D ladder chain with three-connected Ag ions and 4,4′-daps. Complex 5 shows a 2D 4{sup 4}-sql net with Ag ions and 4,4′-daps as 4-connected nodes. Moreover, their solid state luminescence and thermal stabilities also have been investigated. - Graphical abstract: Pictogram: Synthetic procedures of the five anion controlled silver coordination polymers. We reported the synthetic procedures, structure, and luminescence property of the five anion controlled silver coordination polymers based on two novel di(aminophenyl)sulfone V-shaped ligands. Display Omitted - Highlights: • Five new silver coordination polymers were synthesized and characterized. • Two novel designed V-shaped di(aminophenyl)sulfone ligands were first introduced to coordination chemistry. • Anions play important roles in determining the five silver coordination polymers. • The structural diversity and photoluminescence property were also discussed.

  6. Cu{sup II} coordination polymers based on 5-methoxyisophthalate and flexible N-donor ligands: Structures and magnetic properties

    SciTech Connect

    Chang, Xin-Hong; Qin, Jian-Hua; Ma, Lu-Fang; Wang, Li-Ya

    2014-04-01

    Three Cu{sup II} coordination polymers, ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib)]){sub n} (1), ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib){sub 2}]){sub n} (2) and ([Cu(CH{sub 3}O-ip)(bbip)]∙2H{sub 2}O){sub n} (3) (CH{sub 3}O-H{sub 2}ip is 5-methoxyisophthalic acid, bmib is 1,4-bis(2-methylimidazol-1-yl)butane and bbip is 1,3-bis(1H-benzimidazolyl)propane), have been synthesized by hydrothermal methods. Complexes 1–3 were structurally characterized by elemental analysis, infrared (IR) spectra and X-ray single-crystal diffraction. Complex 1 shows a 3D six-connected self-penetrating network based on paddlewheel secondary building units. Complex 2 has a 3-fold interpenetrating 3D diamond framework. Complex 3 possesses a 1D tube-like chain. Thermo-gravimetric and magnetic properties of 1–3 were also investigated. - Graphical abstract: Structures and magnetic properties of copper(II) coordination polymers constructed from 5-methoxyisophthalate linker and two flexible N-donor ancillary ligands. Three copper(II) coordination polymers with 5-methoxyisophthalate and two related flexible N-donor ancillary ligands have been synthesized and structurally characterized. Moreover, thermal behaviors and magnetic properties of these complexes have also been investigated. - Highlights: • Three Cu(II) coordination polymers were synthesized. • The conformations of N-donor ligands and pH value have an effect on the final structures. • The magnetic properties of 1–3 have been investigated.

  7. Restraining the motion of a ligand for modulating the structural phase transition in two isomorphic polar coordination polymers.

    PubMed

    Wang, Bao-Ying; Xu, Wei-Jian; Xue, Wei; Lin, Rui-Biao; Du, Zi-Yi; Zhou, Dong-Dong; Zhang, Wei-Xiong; Chen, Xiao-Ming

    2014-06-28

    A structural phase transition induced by ligand motion was found in a new polar coordination polymer: [Cu(NCS)2(4-APy)2]n (4-APy = 4-aminopyridine). Restraining such motion in an isomorphic compound [Cu(NCS)2(4-MeAPy)2]n (4-MeAPy = 4-methylaminopyridine) results in distinct phase transition behaviour. These findings provide a new clue for modulating phase transition behaviour in known materials.

  8. Stereochemically Distinct Cyclotetrasiloxanes Containing 3-Pyridyl Moieties and Their Functional Coordination Polymers.

    PubMed

    Deshmukh, Mahesh S; Vijayakanth, Thangavel; Boomishankar, Ramamoorthy

    2016-03-21

    Synthesis of new cyclotetrasiloxane scaffolds containing peripherally functionalized 3-pyridyl moieties, [MeSiO(CH═CH(3)Py)]4 (L(1)) and [MeSiO(CH2CH2(3)Py)]4 (L(2)), and their reactivity studies with certain d(10) metal ions are reported. The ligand L(1) is obtained by the Heck-coupling reaction of tetramethyl tetravinyl tetrasiloxane (D4(vi)) and 3-bromopyridine in the presence of the Pd(0) catalysts. The as-synthesized ligand L(1) shows the presence of three stereoisomers, cis-trans-cis (L(1A)), cis-cis-trans (L(1B)), and all-trans (L(1C)), which are quantitatively separated by column chromatography. Subsequent reduction of L(1A), L(1B), and L(1C) with triethylsilane in the presence of catalytic amounts of Pd/C leads to the formation of the ligands L(2A), L(2B), and L(2C) with retention of stereochemistry due to the precursor moieties. Treatment of ZnI2 with L(1A) gives a one-dimensional coordination framework [(L(1A))4(ZnI2)2]∞, 1. These 1D-chains are further connected by π-π stacking interactions between the pyridyl groups of the adjacent chains leading to the formation of a three-dimensional network with the topology of a PtS net. The reaction of silver nitrate with ligand L(1B) gives a chain like one-dimensional cationic coordination polymer {[(L(1B))4Ag2]·2NO3·H2O·CH3OH }∞, 2, consisting of two different kinds of 32-membered macrocycles. Treatment of the all-trans ligand L(2C) with copper(I) iodide salt results in the formation of a cubane-type Cu4I4 cluster MOF [(L(2C))4Cu4I4]∞, 3, in a two-dimensional 4-connected uninodal sql/Shubnikov tetragonal plane net topology represented by the Schläfli symbol {4(4).6(2)}. This MOF displays a thermochromic luminescence behavior due to Cu4I4 clusters showing an orange emission at 298 K and a blue emission at 77 K. PMID:26958986

  9. Zirconium(IV)-Benzene Phosphonate Coordination Polymers: Lanthanide and Actinide Extraction and Thermal Properties.

    PubMed

    Luca, Vittorio; Tejada, Juan J; Vega, Daniel; Arrachart, Guilhem; Rey, Cyrielle

    2016-08-15

    Coordination polymers with different P/(Zr + P) molar ratios were prepared by combining aqueous solutions of Zr(IV) and benzenephosphonate derivatives. 1,3,5-Benzenetrisphosphonic acid (BTP) as well as phosphonocarboxylate derivatives in which carboxylate substitutes one or two of the phosphonate groups were chosen as the building blocks. The precipitates obtained on combining the two solutions were not X-ray amorphous but rather were indicative of poorly ordered materials. Hydrothermal treatment did not alter the structure of the materials produced but did result in improved crystalline order. The use of HF as a mineralizing agent during hydrothermal synthesis resulted in the crystallization of at least three relatively crystalline phases whose structure could not be determined owing to the complexity of the diffraction patterns. Gauging from the similarity of the diffraction patterns of all the phases, the poorly ordered precipitates and crystalline materials appeared to have similar underlying structures. The BTP-based zirconium phosphonates all showed a higher selectivity for lanthanides and thorium compared with cations such as Cs(+), Sr(2+), and Co(2+). Substitution of phosphonate groups by carboxylate groups did little to alter the pattern of selectivity implying that selectivity in the system was entirely determined by the -POH group with little influence from the -COOH groups. Samples with the highest phosphorus content showed the highest extraction efficiencies for lanthanide elements, especially the heavy lanthanides such as Dy(3+) and Ho(3+) with separation factors of around four with respect to La(3+). In highly acid solutions (4 M HNO3) there was a pronounced variation in extraction efficiency across the lanthanide series. In situ, nonambient diffraction was performed on ZrBTP-0.8 loaded with Th, Ce, and a complex mixture of lanthanides. In all cases the crystalline Zr2P2O7 pyrophosphate phase was formed at ∼800 °C demonstrating the versatility of

  10. Zirconium(IV)-Benzene Phosphonate Coordination Polymers: Lanthanide and Actinide Extraction and Thermal Properties.

    PubMed

    Luca, Vittorio; Tejada, Juan J; Vega, Daniel; Arrachart, Guilhem; Rey, Cyrielle

    2016-08-15

    Coordination polymers with different P/(Zr + P) molar ratios were prepared by combining aqueous solutions of Zr(IV) and benzenephosphonate derivatives. 1,3,5-Benzenetrisphosphonic acid (BTP) as well as phosphonocarboxylate derivatives in which carboxylate substitutes one or two of the phosphonate groups were chosen as the building blocks. The precipitates obtained on combining the two solutions were not X-ray amorphous but rather were indicative of poorly ordered materials. Hydrothermal treatment did not alter the structure of the materials produced but did result in improved crystalline order. The use of HF as a mineralizing agent during hydrothermal synthesis resulted in the crystallization of at least three relatively crystalline phases whose structure could not be determined owing to the complexity of the diffraction patterns. Gauging from the similarity of the diffraction patterns of all the phases, the poorly ordered precipitates and crystalline materials appeared to have similar underlying structures. The BTP-based zirconium phosphonates all showed a higher selectivity for lanthanides and thorium compared with cations such as Cs(+), Sr(2+), and Co(2+). Substitution of phosphonate groups by carboxylate groups did little to alter the pattern of selectivity implying that selectivity in the system was entirely determined by the -POH group with little influence from the -COOH groups. Samples with the highest phosphorus content showed the highest extraction efficiencies for lanthanide elements, especially the heavy lanthanides such as Dy(3+) and Ho(3+) with separation factors of around four with respect to La(3+). In highly acid solutions (4 M HNO3) there was a pronounced variation in extraction efficiency across the lanthanide series. In situ, nonambient diffraction was performed on ZrBTP-0.8 loaded with Th, Ce, and a complex mixture of lanthanides. In all cases the crystalline Zr2P2O7 pyrophosphate phase was formed at ∼800 °C demonstrating the versatility of

  11. Two novel metal–organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

    SciTech Connect

    Niu, Qing-Jun; Zheng, Yue-Qing Zhou, Lin-Xia; Zhu, Hong-Lin

    2015-07-15

    Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H{sub 2}en)[Co{sub 3}(H{sub 2}zdn){sub 2}(ox)(H{sub 2}O){sub 2}] (1) and Cd{sub 2}(H{sub 2}zdn)(ox){sub 0.5}(H{sub 2}O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H{sub 5}zdn; oxalic acid=H{sub 2}ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O–P–O units of H{sub 5}zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property. - Graphical abstract: Linked by oxalate, two zoledronate-based metal–organic frameworks are synthesized, which exhibits the different frameworks. Magnetism and luminescent properties have been studied. The weak antiferromagnetic coupling is conducted in 1. - Highlights: • Compound 1 and 2 are first linked by oxalate anion based on zoledronic acid. • Compound 1 generates a classic “dia Diamond” (6{sup 6}) topology. • Compound 2 exhibits a (4{sup 4}·6{sup 2})(4{sup 4}·6{sup 6}) topology. • Magnetism and luminescent properties of 1 and 2 have been studied, respectively.

  12. New 3-D coordination polymers based on semi-rigid V-shape tetracarboxylates

    NASA Astrophysics Data System (ADS)

    Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning; Yu, Jie-Hui; Zhang, Ping; Xu, Ji-Qing

    2015-03-01

    Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N‧-donor ligands yielded three new coordination polymers as [Cu4(fph)2(bpe)3(H2O)2]·2H2O (fph=4,4‧-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co2(fph)(bpa)2(H2O)2]·3H2O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H2O)(H2oph)(bpa)] (oph=4,4‧-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu2+ ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co2+ ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1-3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors.

  13. The role of IAEA in coordinating research and transferring technology in radiation chemistry and processing of polymers

    NASA Astrophysics Data System (ADS)

    Haji-Saeid, M.; Sampa, M. H.; Ramamoorthy, N.; Güven, O.; Chmielewski, A. G.

    2007-12-01

    The IAEA has been playing a significant role in fostering developments in radiation technology in general and radiation processing of polymers in particular, among its Member States (MS) and facilitate know-how/technology transfer to developing MS. The former is usually achieved through coordinated research projects (CRP) and thematic technical meetings, while the latter is mainly accomplished through technical cooperation (TC) projects. Coordinated research projects encourage research on, and development and practical application of, radiation technology to foster exchange of scientific and technical information. The technical cooperation (TC) programme helps Member States to realize their development priorities through the application of appropriate radiation technology. The IAEA has implemented several coordinated research projects (CRP) recently, including one on-going project, in the field of radiation processing of polymeric materials. The CRPs facilitated the acquisition and dissemination of know-how and technology for controlling of degradation effects in radiation processing of polymers, radiation synthesis of stimuli-responsive membranes, hydrogels and absorbents for separation purposes and the use of radiation processing to prepare biomaterials for applications in medicine. The IAEA extends cooperation to well-known international conferences dealing with radiation technology to facilitate participation of talented scientists from developing MS and building collaborations. The IAEA published technical documents, covering the findings of thematic technical meetings (TM) and coordinated research projects have been an important source of valuable practical information.

  14. Highly efficient stabilisation of meta-ethynylpyridine polymers with amide side chains in water by coordination of rare-earth metals.

    PubMed

    Makida, Hiroki; Abe, Hajime; Inouye, Masahiko

    2015-02-14

    An amphiphilic meta-ethynylpyridine polymer with chiral amide side chains was developed. The polymer was prepared by sequential Sonogashira reactions, and the product was soluble in polar and apolar solvents. The additive effects of metal salts on the polymer were examined in water and aqueous EtOH on the basis of UV-vis and CD spectra. The enhancement of the positive Cotton effect and hypochromism around 360 nm occurred by the addition of various metal salts, indicating the coordination of the cations to the amide side chains of the polymer to stabilise the helical structure. Among them, rare-earth metal salts, especially Sc(OTf)3 showed more efficient additive effects probably because of its strong coordination ability even in water. Positive cooperativity was observed for the coordination of Sc(OTf)3 to the polymer in aqueous EtOH.

  15. Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

    NASA Astrophysics Data System (ADS)

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-Li

    2013-09-01

    Three new metal-organic coordination polymers [Co(4-bbc)2(bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H2O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H2pdc=3,5-pyridinedicarboxylic acid, 1,4-H2ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and CoII ions. Polymer 2 exhibits a 2D network with a (3·4·5)(32·4·5·62·74) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1-3. Moreover, the thermal stability, electrochemical and luminescent properties of 1-3 were investigated.

  16. Polymer complexes. LIV. Structural and spectral studies of supramolecular coordination polymers built from Ni(II), Fe(II) and Pd(II) with sulphadrug

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Belal, A. A. M.; Diab, M. A.; Mohamed, R. H.

    2011-03-01

    Polymer complexes of p-acrylamidyl sulphaguanidine (HL) with Ni(II), Fe(II) and Pd(II) salts have been prepared. The structures of the polymer complexes were elucidated using elemental analysis, 1H NMR, UV-Vis, IR spectroscopies, magnetic moment, molar conductance and thermal analysis. The polymer complexes were isolated in 1:1 and 1:2 (M:L) ratios. The solid monocomplexes (1:1) (M:L) were isolated in the general formula [Fe(HL)O 2SO 2(OH 2) 2]. The biscomplexes (1:2) (M:L) solid chelates found to have the general formula [Ni(HL) 2X 2] n (X = Cl -, Br -, I -, NO3-, NCS -), [Fe(HL)(en)(OSO 3)(OH 2)] n and [Ni(HL) 2(Py) 2] nX 2, while {[Pd(L)X] 2} n (1:1) (X = Cl - or Br -). In all the polymer complexes the ligand and anions were found to be coordinated to the Ni(II) and Fe(II) ions. The bidentate nature of the ligand is evident from IR spectra. The magnetic and spectroscopic data indicate a octahedral geometry for complexes. The thermal behaviour of these chelates shows that the hydrated complexes loss water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps.

  17. Control of water molecule aggregations in copper 1,4-cyclohexanedicarboxylate coordination polymers containing pyridyl-piperazine type ligands

    NASA Astrophysics Data System (ADS)

    Qiblawi, Sultan H.; LaDuca, Robert L.

    2014-01-01

    A series of layered divalent copper coordination polymers containing 1,4-cyclohexanedicarboxylate and long-spanning pyridyl-piperazine type ligands exhibits greatly different co-crystallized water molecule aggregations depending on the specific ligands used. Both [Cu(t-14cdc)(4-bpmp)]n (1, t-14cdc = trans-1,4-cyclohexanedicarboxylate, 4-bpmp = bis(4-pyridylmethyl)piperazine) and {[Cu(t-14cdc)(4-bpfp)(H2O)2]·6H2O}n (2, 4-bpfp = bis(4-pyridylformyl)piperazine) possess 2D (4,4) coordination polymer grids. However 1 lacks any co-crystallized water and has pinched grid apertures, while 2 manifests infinite water tapes with T6(2)4(2) classification and rectangular grid apertures. {[Cu2(c-14cdc)2(4-bpmp)]·2H2O}n (3, c-14cdc = cis-1,4-cyclohexanedicarboxylate) has [Cu2(c-14cdc)]2 ribbons with paddlewheel dimeric units linked into 2D slabs by 4-bpmp tethers, along with isolated water molecule pairs. In contrast, {[Cu2(c-14cdc)2(4-bpfp)]·10H2O}n (4) shows a very similar underlying coordination polymer topology but entrains unique decameric water molecule clusters. The minor product {[Cu2(c-14cdcH)2(t-1,4-cdc)(4-bpfp)2(H2O)2]·2H2O}n (5) was isolated along with 4; this compound underwent some in situ cis to trans cyclohexane-dicarboxylate ligand isomerization and exhibits a ladder polymer motif.

  18. Exploring control of cadmium halide coordination polymers via control of cadmium(II) coordination sites utilizing short multidentate ligands

    NASA Astrophysics Data System (ADS)

    Hines, C. Corey; Reichert, W. Matthew; Griffin, Scott T.; Bond, Andrew H.; Snowwhite, Paul E.; Rogers, Robin D.

    2006-08-01

    The goal of this project has been to determine the capability of a number of linear multidentate ligands to induce extended structures in cadmium halides. Metal salts of the form CdX 2 (X=Cl, Br, I), and for comparison Cd(NO 3) 2, were complexed with diethylene glycol (EO2), triethylene glycol monomethyl ether (EO3Me), triethylene glycol dimethyl ether (a glyme, EG3), diethylene triamine (EN2), and 1,3-propylenediamine (PN1). The crystal structures of 11 resulting complexes were structurally characterized including: [Cd(EO2) 3][Cd 2I 6], [Cd(EN2) 2]Cl 2·H 2O, [Cd(EN2) 2]Br 2, [Cd(EN2) 2][CdI 4], [CdCl 2(EO3Me)] 2, [CdBr 2(EO3Me)] 2, [Cd(NO 3) 2(EO3Me)], [(CdCl 2) 2(EG3)] n, [(CdBr 2) 2(EG3)] n, [CdI 2(EG3)], and [CdI 2(PN1)] n. While each structure is interesting in its own right, the continued observance of a wide variety of coordination modes for such similar ligands does little to help improve the predictability of simple Cd 2+ coordination compounds.

  19. Copper(II)-lanthanide(III) coordination polymers constructed from pyridine-2,5-dicarboxylic acid: Preparation, crystal structure and photoluminescence

    NASA Astrophysics Data System (ADS)

    Xia, Zheng-Qiang; Wei, Qing; Chen, San-Ping; Feng, Xin-Ming; Xie, Gang; Qiao, Cheng-Fang; Zhang, Guo-Chun; Gao, Sheng-Li

    2013-01-01

    A series of 3d-4f heterometallic coordination polymers, formulated as {[Cu3Ln2(pydc)6(H2O)12]·4H2O}n [Ln=Tb (1), Eu (2), Dy (3), Ho (4), Lu (5)], {[CuNd2(pydc)4(H2O)3]·H2O}n (6) and {[Cu3Pr2(pydc)6(H2O)13]·4H2O}n (7) (where H2pydc=pyridine-2,5-dicarboxylic acid), have been hydrothermally prepared by reactions of H2pydc ligand with lanthanide ions in the presence of Cu(II) ion. X-ray crystal structure analysis reveals that these compounds exhibit rich structural chemistry. 1-5 are isomorphous and present a two-dimensional network constructed from Ln2Cu2L2(H2O)2 SBU rings and CuL2(H2O) building blocks. In 6, two-dimensional ladder-like layers based on Nd(III) belts and CuL2O2 units are assembled by H2pydc ligands into a three-dimensional open framework. Polymer 7 displays a two-dimensional wave-like layer structure containing two distinct ring units, in which a new coordination mode of the pydc2- ligand is observed. The results indicate that the coordination flexibility of the pydc2- ligand and lanthanide contraction effect play cooperative roles in the formation of coordination polymers with different polymeric architectures. Compounds 1-2 exhibit intense green and red luminescence emission characteristics of Tb(III) and Eu(III), respectively. Furthermore, elemental analyses (EA), infrared spectra (IR) and thermogravimetric analyses (TGA) of these compounds were also studied.

  20. Anion Effects on Lanthanide(III) Tetrazole-1-acetate Dinuclear Complexes Showing Slow Magnetic Relaxation and Photofluorescent Emission.

    PubMed

    Lu, Ying-Bing; Jiang, Xiao-Ming; Zhu, Shui-Dong; Du, Zi-Yi; Liu, Cai-Ming; Xie, Yong-Rong; Liu, Liang-Xian

    2016-04-18

    Three types of lanthanide complexes based on the tetrazole-1-acetic acid ligand and the 2,2'-bipyridine coligand were prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analyses; the formulas of these complexes are [Ln2(1-tza)4(NO3)2(2,2'-bipy)2] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5)), [Dy2(1-tza)4Cl2(2,2'-bipy)2] (6), and [Yb2(1-tza)4(NO3)2(2,2'-bipy)2] (7) (1-tza = tetrazole-1-acetate and 2,2'-bipy = 2,2'-bipyridine). They are dinuclear complexes possessing similar structures but different lanthanide(III) ion coordination geometries because of the distinction of peripheral anions (such as NO3(-) and Cl(-)) and the effect of lanthanide contraction. The variable-temperature magnetic susceptibilities of 1-6 were measured. Both Dy(III) complexes (5 and 6) display field-induced single-molecule magnet behaviors. Ab initio calculations revealed that the Dy(III) complex 6 possesses a more anisotropic Dy(III) ion in comparison to that in 5. The room-temperature photoluminescence spectra of Sm(III) (1), Eu(III) (2), Tb(III) (4), and Dy(III) (5 and 6) complexes exhibit strong characteristic emissions in the visible region, whereas the Yb(III) (7) complex shows near-infrared (NIR) luminescence. PMID:27023680

  1. Vapochromic Behaviour of M[Au(CN)2]2-Based Coordination Polymers (M = Co, Ni)

    PubMed Central

    Lefebvre, Julie; Korčok, Jasmine L.; Katz, Michael J.; Leznoff, Daniel B.

    2012-01-01

    A series of M[Au(CN)2]2(analyte)x coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), pyridine; x = 2 or 4) was prepared and characterized. Addition of analyte vapours to solid M(μ-OH2)[Au(CN)2]2 yielded visible vapochromic responses for M = Co but not M = Ni; the IR νCN spectral region changed in every case. A single crystal structure of Zn[Au(CN)2]2(DMSO)2 revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II) salt and K[Au(CN)2] in DMSO yielded the isostructural Ni[Au(CN)2]2(DMSO)2 product. Co[Au(CN)2]2(DMSO)2 and M[Au(CN)2]2(DMF)2 (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH2)[Au(CN)2]2 and from DMSO or DMF solution synthesis. Co[Au(CN)2]2(pyridine)4 is generated via vapour absorption by Co(μ-OH2)[Au(CN)2]2; the analogous Ni complex is synthesized by immersion of Ni(μ-OH2)[Au(CN)2]2 in 4% aqueous pyridine. Similar immersion of Co(μ-OH2)[Au(CN)2]2 yielded Co[Au(CN)2]2(pyridine)2, which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH2)[Au(CN)2]2 was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN)2]2 was prepared by dehydration of Co(μ-OH2)[Au(CN)2]2 at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate. PMID:22737031

  2. Different aliphatic dicarboxylates affected assemble of new coordination polymers constructed from flexible-rigid mixed ligands

    SciTech Connect

    Xu Xinxin; Ma Ying; Wang Enbo

    2007-11-15

    In this article, seven coordination polymers: [Cd(C{sub 5}H{sub 6}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (1), [Zn(C{sub 5}H{sub 6}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (2), [Cd(C{sub 6}H{sub 8}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (3), {l_brace}[Mn(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O){sub 4}] (C{sub 4}H{sub 4}O{sub 4}).4H{sub 2}O{r_brace}{sub n} (4), [Mn{sub 5}(C{sub 4}H{sub 4}O{sub 4}){sub 4}(O)]{sub n} (5), [Cd(C{sub 4}H{sub 4}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O)]{sub n} (6) and [Zn(C{sub 6}H{sub 6}O{sub 4})(C{sub 12}H{sub 8}N{sub 2})(H{sub 2}O)]{sub n} (7) were synthesized and characterized by single-crystallographic X-ray diffraction. Compounds 1 and 2 are two-dimensional layers connected by glutarate anions and 4,4'-bpy. Unlike compounds 1 and 2, compound 3 is a two-fold interpenetration network. Compound 4 is a one-dimensional chain-like structure, which is further extended to two-dimensional supramolecular layer structure with hydrogen bond. During the synthesis of compound 4, to our surprise, we got compound 5; compound 5 is an interesting three-dimensional network composed of pentanuclear Mn(II) building units and succinate anions. Compound 6 is also a two-dimensional supramolecular layer structure composed of one-dimensional chain-like structure with hydrogen bonds and {pi}-{pi} interactions. Compound 7 is also a one-dimensional chain-like structure, which is further connected with the same kind of interaction to generate two-dimensional supramolecular layer structure. Furthermore, compounds 1 and 2 both exhibit fluorescent property at room temperature. - Graphical abstract: Seven complexes composed by 3D metal ions, aliphatic acid ligand and rigid bidentate nitrogen ligands: 4,4'-bpy, 2,2'-bpy and 1,10'-phen. With the change of the carbon number of the backbone of aliphatic dicarboxylate ligand, we can synthesize different complexes with various structures.

  3. Photo- and thermochromic and adsorption properties of porous coordination polymers based on bipyridinium carboxylate ligands.

    PubMed

    Toma, Oksana; Mercier, Nicolas; Allain, Magali; Kassiba, Abdel Adi; Bellat, Jean-Pierre; Weber, Guy; Bezverkhyy, Igor

    2015-09-21

    The zwitterionic bipyridinium carboxylate ligand 1-(4-carboxyphenyl)-4,4'-bipyridinium (hpc1) in the presence of 1,4-benzenedicarboxylate anions (BDC(2-)) and Zn(2+) ions affords three porous coordination polymers (PCPs): [Zn5(hpc1)2(BDC)4(HCO2)2]·2DMF·EtOH·H2O (1), [Zn3(hpc1)(BDC)2(HCO2)(OH)(H2O)]·DMF·EtOH·H2O (2), and [Zn10(hpc1)4(BDC)7(HCO2)2(OH)4(EtOH)2]·3DMF·3H2O (3), with the formate anions resulting from the in situ decomposition of dimethylformamide (DMF) solvent molecules. 1 and 3 are photo- and thermochromic, turning dark green as a result of the formation of bipyridinium radicals, as shown by electron paramagnetic resonance measurements. Particularly, crystals of 3 are very photosensitive, giving an eye-detectable color change upon exposure to the light of the microscope in air within 1-2 min. A very nice and interesting feature is the regular discoloration of crystals from the "edge" to the "core" upon exposition to O2 (reoxidation of organic radicals) due to the diffusion of O2 inside the pores, with this discoloration being slower in an oxygen-poor atmosphere. The formation of organic radicals is explained by an electron transfer from the oxygen atoms of the carboxylate groups to pyridinium cycles. In the structure of 3', [Zn10(hpc1)4(BDC)7(OH)6(H2O)2], resulting from the heating of sample 3 (desolvation and loss of CO molecules due to the decomposition of formate anions), no suitable donor-acceptor interaction is present, and as a consequence, this compound does not exhibit any chromic properties. The presence of permanent porosity in desolvated 1, 2, and 3' is confirmed by methanol adsorption at 25 °C with the adsorbed amount reaching 5 wt % for 1, 10 wt % for 3', and 13 wt % for 2. The incomplete desorption of methanol at 25 °C under vacuum points to strong host-guest interactions. PMID:26370743

  4. Influence of the counter ion on the structure of two new copper(I) coordination polymers: Synthesis, structural characterization and thermal analysis

    NASA Astrophysics Data System (ADS)

    Beheshti, Azizolla; Nobakht, Valiollah; Carlucci, Lucia; Proserpio, Davide M.; Abrahams, Carmel

    2013-04-01

    Two new coordination polymers [Cu2(μ3-SCN)2(μ-bbd)]n (1) and {[Cu(μ-bbd)1.5](PF6)}n (2) were synthesized by the reactions of 1,4-bis(3,5-dimethylpyrazol-1-yl)butane (bbd) with the corresponding copper(I) salts, in order to evaluate the effect of the counter anion on the structure of the resulting products. The structure of these compounds were determined by X-ray crystallography; Compound 1 is a 2D coordination polymer, in which the thiocyanate ligand adopts uncommon μ3-1κ1N;2:3κ2S coordination mode to link three tetrahedrally coordinated copper centers. The fourth coordination site on each copper atom is occupied by a pyrazole nitrogen atom belonging to a μ-bbd ligand. In contrast to 1, 2 is a 1D chain coordination polymer in which the copper atoms, adopting a distorted trigonal planar geometry, are linked by bridging bbd ligands having alternately two different conformations. The results indicate that the use of a coordinating counter anion as thiocyanate which is capable of bridging more than one metal center instead of non-coordinating hexafluorophosphate anion, promotes the formation of a 2D polymer over a 1D polymeric chain. The complexes have also been characterized by elemental analysis, IR spectroscopy, XRPD and thermal analysis.

  5. Design of a multi-coordinating polymer as a platform for functionalizing metal, metal oxide and semiconductor nanocrystals

    NASA Astrophysics Data System (ADS)

    Wang, Wentao; Ji, Xin; Kapur, Anshika; Mattoussi, Hedi

    2016-03-01

    We introduce a new set of amphiphilic polymers as multifunctional, metal-coordinating ligands adapted to surfacefunctionalize quantum dots (QDs), iron oxide nanoparticles (IONPs) and gold nanoparticles/nanorods (AuNPs/AuNRs). The ligand design relies on the introduction of several anchoring groups, hydrophilic moieties and reactive functionalities into a polymer chain, via one-step nucleophilic addition reaction. Such synthetic scheme also allows the insertion of target biomolecules during the ligand synthesis. This functionalization strategy yields nanocrystals that exhibit long-term colloidal stability over a broad range of biological conditions, such as pH changes and when mixed with growth media. When zwitterion groups are used as hydrophilic motifs, this provides compact nanocrystals that are compatible with conjugation to proteins via metal-polyhistidine self-assembly. In addition, we show that QDs ligated with these polymers can engage in energy or charge transfer interactions. Furthermore, nanocrystals coated with folic acid-modified polymers could promote the delivery of nanoparticle-conjugates into cancer cells via folate receptormediated endocytosis.

  6. Five new Mn(II)/Co(II) coordination polymers constructed from flexible multicarboxylate ligands with varying magnetic properties

    SciTech Connect

    Liu, Sui-Jun; Zeng, Yong-Fei; Hu, Xin; Xue, Li; Han, Song-De; Jia, Ji-Min; Hu, Tong-Liang

    2013-08-15

    Five new Mn(II)/Co(II) coordination polymers [Mn{sub 2}(Adi){sub 2}(DMA)]{sub n} (1), [Mn{sub 2}(Adi){sub 2}(DMF)]{sub n} (2), [Mn{sub 4}(Adi){sub 4}(DMF){sub 2}]{sub n} (3), [Co{sub 4}(Adi){sub 4}(DMF){sub 2}]{sub n} (4) and ([Co{sub 3}(Cit){sub 2}(H{sub 2}O){sub 3}]·(H{sub 2}O)){sub n} (5) [Adi=adipate anion, Cit=citrate anion, DMA=N,N′-dimethylacetamide and DMF=N,N′-dimethylformamide] have been successfully constructed from two flexible multicarboxylate ligands under solvothermal conditions. Complexes 1 and 2 exhibit 2-D network featured 1-D Mn{sup II} chain, 3 and 4 are 3-D frameworks containing different 1-D carboxylate–metal chain, while 5 shows a 3-D structure based on Co{sub 6} wheel clusters. Magnetic investigations indicate antiferromagnetic behaviors for 1–4 and weak ferromagnetic behavior for 5 because of distinct linkage modes of metal ions. - Graphical abstract: Five new Mn(II)/Co(II) coordination polymers display 2-D/3-D structures containing 1-D carboxylate–metal chains or wheel clusters. Magnetic analyses reveal that they show antiferromagnetic, canted antiferromagnetic and weak ferromagnetic behaviors, respectively. Highlights: ●Five new Mn(II)/Co(II) coordination polymers have been synthesized. ●A complex-based Co{sub 6} wheel cluster was obtained. ●The different magnetic properties of the complexes are discussed.

  7. Syntheses and structures of three heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid

    SciTech Connect

    Fang, Wei-Hui; Yang, Guo-Yu

    2014-04-01

    Three lanthanide–transition-metal coordination polymers, namely, [Er{sub 2}L{sub 6}(H{sub 2}O)][Cu{sub 2}I{sub 2}] (1), [ErL{sub 3}][CuI] (2), and [Dy{sub 2}L{sub 6}(BPDC){sub 0.5}(H{sub 2}O){sub 4}][Cu{sub 3}I{sub 2}] (3) (HL=4-pyridin-3-yl-benzoic acid, H{sub 2}BPDC=4,4′-biphenyldicarboxylic acid) have been made by reacting Ln{sub 2}O{sub 3} and CuI with HL at different temperatures under hydrothermal conditions. All the complexes are characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction, respectively. 1–3 all construct from dimeric (Ln{sub 2}) and (Cu{sub 2}) units and exhibit two types of the structural features: 1 is a two-dimensional layer, 2–3 are three-dimensional frameworks. Interestingly, the in situ formation of the BPDC ligand is found in the structure of 3. The distinct architectures of these complexes indicated that the reaction temperature plays an important role in the formation of higher dimensional coordination polymers. - Graphical abstract: By hydrothermal reaction of lanthanide oxide, copper halide, and 4-pyridin-3-yl-benzoic ligand at different temperatures, a series of 1-D to 3-D 3d–4f coordination polymers, namely [ErL{sub 3}(H{sub 2}O){sub 2}][CuI], [Er{sub 2}L{sub 6}(H{sub 2}O)][Cu{sub 2}I{sub 2}], [ErL{sub 3}][CuI], and [Dy{sub 2}L{sub 6}(BPDC){sub 0.5}(H{sub 2}O){sub 4}][Cu{sub 3}I{sub 2}], have been made, respectively. - Highlights: • Three novel heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid have been hydrothermally synthesized. • Mixed dinuclear motifs of (Ln{sub 2}) and (Cu{sub 2}) serve as secondary building units to generate 2-D layer and 3-D frameworks. • It is proved that higher temperature is apt to permit construction of high dimensional architectures.

  8. Effects of isomorphous substitution of a coordination polymer on the properties and its application in electrochemical sensing

    SciTech Connect

    Zhou, Bo; Liang, Li-Mei; Yao, Jie

    2014-07-01

    This work concerns the isomorphous substitution of coordination polymers (CPs) and its effect on the optical and electrochemical properties. The application of CPs in electrochemical sensing was studied as well. Isomorphous coordination polymers, [Co{sub x}Zn{sub 1−x}tyr]{sub n} (tyr=L-tyrosine), where x (0–1) was controlled by the Co/Zn ratios of raw materials, were successfully synthesized via a hydrothermal method, as proved by XRD and EDS results. Their UV–vis DRS and fluorescence spectra change gradually along with the composition. Cyclic voltammograms of modified electrodes, [Co{sub x}Zn{sub 1−x}tyr]{sub n}/GCE, show that as more and more Zn replaced Co, the current signal decreases greatly and the potential shifts negatively. Much attention was paid to [Cotyr]{sub n} due to its highest sensitivity. Refreshable modified carbon paste electrode, [Cotyr]{sub n}-CPE, was used to determine nitrite, and showed pretty good performance as evidenced by chronoamperometry. The response was made very fast within mere 5 s. The linear detection range was from 5.00×10{sup −5} to 3.45×10{sup −3} M, with sensitivity of 263.4 mA mol{sup −1} L cm{sup −2}. The detection limit was found to be 2.00×10{sup −5} M. The sensor also showed good antiinterference and reproducibility. - Graphical abstract: Evolution of the optical and electrochemical properties of isomorphic coordination polymers [Co{sub x}Zn{sub 1−x}tyr]{sub n} along with the changing of x was studied. The CP also showed perfect performance in the electrochemical determination of nitrite. - Highlights: • Isomorphous substitution of coordination polymers (CPs). • Substitution-caused evolution of optical and electrochemical properties of CPs. • Application of CPs in electrochemical sensing, an incipient area. • Perfect performance of CPs in electrochemical determination of nitrite.

  9. Controlled formation of fluorescent metalloporphyrin-containing coordination polymer particles from seed structures by designed shape-transformation reactions.

    PubMed

    Sun, Yu; Li, Xiaopeng; Caravella, Alessio; Gao, Rongke

    2015-04-27

    Herein, nanorod structures and four-leaf clover structures of fluorescent zinc 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (ZnTPyP)-containing coordination polymer particles (CPPs) were first synthesized by a bottom-up strategy assisted by surfactants and then employed as seed structures for further shape-transformation reactions. We have successfully designed the morphological transformation for different dimensions, achieving the controlled formation of octahedron structures at both the nanometer scale and micrometer scale from the seed structures. Our approach illustrates a new method to design and synthesize metalloporphyrin-containing CPPs in a systematic and controllable manner.

  10. Coordination polymers of Ag(I) based on iminocarbene ligands involving metal-carbon and metal-heteroatom interactions

    NASA Astrophysics Data System (ADS)

    Netalkar, Sandeep P.; Netalkar, Priya P.; Revankar, Vidyanand K.

    2016-03-01

    The reaction of Ag2O with three novel imino-NHC ligands derived from 2-chloroacetophenone with pendant N-donor functional group incorporated by reaction with methoxyamine and 1-methyl/ethyl/n-butyl-substituted imidazoles afforded one-dimensional coordination polymers with [(-NHCarbene)Ag(NHCarbene-)PF6]n formulation involving both carbon-metal and heteroatom-metal interactions, the carbon and heteroatom involved in coordination to silver being from different molecule of the ligand. The complexes as well as the ligands were characterized by spectroscopic methods as well as the solid state structures determined in case of 2a, 3a and complex 5. The iminocarbene ligands serve as non-chelating building block for supramolecular silver assemblies.

  11. A Crystalline Copper(II) Coordination Polymer for the Efficient Visible-Light-Driven Generation of Hydrogen.

    PubMed

    Dong, Xi-Yan; Zhang, Mei; Pei, Ru-Bo; Wang, Qian; Wei, Dong-Hui; Zang, Shuang-Quan; Fan, Yao-Ting; Mak, Thomas C W

    2016-02-01

    A crystalline coordination polymer (CP) photocatalyst (Cu-RSH) which combines redox-active copper centers with photoactive rhodamine-derived ligands remains stable in acid and basic solutions from pH 2 to 14, and efficiently catalyzes dihydrogen evolution at a maximum rate of 7.88 mmol g(-1)  h(-1) in the absence of a mediator and a co-catalyst. Cyclic voltammetry, control experiments, and DFT calculations established that copper nodes with open coordination sites and favorable redox potentials, aided by spatially ordered stacking of rhodamine-based linkers, account for the high catalytic performance of Cu-RSH. Emission quenching, time-resolved fluorescence decay, and transient photocurrent experiments disclosed the charge separation and transfer process in the catalytic system. The present study demonstrates the potential of crystalline copper CPs for the practical utilization of light. PMID:26709609

  12. Designing Tunable White-Light Emission from an Aurophilic Cu(I) /Au(I) Coordination Polymer with Thioether Ligands.

    PubMed

    Ovens, Jeffrey S; Christensen, Peter R; Leznoff, Daniel B

    2016-06-01

    White-light emitters have attracted considerable attention due to their importance in current and future technologies. By incorporating molecular fragments that independently emit in the blue, green/yellow, and red visible regions, specifically Cu-NC, Au⋅⋅⋅Au interactions, and Cu-SR2 , respectively, into a single material, new white-light-emitting systems have been targeted. With this goal, three new Cu(I) /thioether-based coordination polymers containing bridging [Au(CN)2 ](-) units have been synthesized and structurally characterized, and their photoluminescence properties (at room and low temperatures) have been delineated. Using this approach, white-light emission (tunable from slightly yellow to slightly blue, depending on λex ) is generated from Cu(Me2 S)[Au(CN)2 ], a feature uncommon in such simple coordination compounds. PMID:27138305

  13. N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

    NASA Astrophysics Data System (ADS)

    Zhuang, Gui-lin; Chen, Wu-lin; Zheng, Jun; Yu, Hui-you; Wang, Jian-guo

    2012-08-01

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H3SIDA) and Ln(NO3)3 (Ln=La, 1; Pr, 2; Nd, 3; Gd, 4). Crystal structure analysis exhibits that lanthanide ions affect the coordination number, bond length and dimension of compounds 1-4, which reveal that their structure diversity can be attributed to the effect of lanthanide contraction. Furthermore, the combination of magnetic measure with quantum Monte Carlo(QMC) studies exhibits that the coupling parameters between two adjacent Gd3+ ions for anti-anti and syn-anti carboxylate bridges are -1.0×10-3 and -5.0×10-3 cm-1, respectively, which reveals weak antiferromagnetic interaction in 4.

  14. Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries

    DOE PAGES

    Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.; Shkrob, Ilya A.; Abraham, Daniel P.

    2016-03-31

    Fluorinated carbonate solvents are pursued as liquid electrolytes for high-voltage Li-ion batteries. We report aggregation of [Li+(FEC)3]n polymer species from fluoroethylene carbonate containing electrolytes and scrutinized the causes for this behavior.

  15. Four homochiral coordination polymers contain N-acetyl-L-tyrosine and different N-donor ligand: Influence of metal cations, ancillary ligands and coordination modes

    NASA Astrophysics Data System (ADS)

    Li, Meng-Li; Song, Hui-Hua

    2013-10-01

    Using the chiral ligand N-acetyl-L-tyrosine (Hacty) and maintaining identical reaction conditions, Zn(II), Co(II), and Cd(II) salts provided four novel homochiral coordination polymers {[Zn(acty)(bipy)2(H2O)2]·NO3·2H2O}n1, {[Co(acty)(bipy)2(H2O)2]·NO3·2H2O}n2, {[Cd(acty)2(bipy)H2O]·H2O}n3, and {[Cd(acty)(bpe)2(Ac)]·6H2O}n4 (bipy=4,4‧-bipyridine; bpe=1,2-di(4-pyridyl)ethane) in the presence of ancillary ligands. Compounds 1 and 2 are isostructural 1D chain structures. The neighboring chains are further linked into a 3D supramolecular structure via π⋯π stacking and hydrogen bond interactions. Compound 3 shows a 2D network and 4 generates 1D infinite chains along the c-axis. Compounds 3 and 4 are further connected into 3D supramolecular network by hydrogen bond interactions. More importantly, coordination in acyl oxygen atoms and ancillary ligands (bpe) as monodentate decorating ligands in 4 are rarely reported. Ancillary ligands and metal cations significantly influence the structure of the complexes. The photoluminescence properties of 1, 3, and 4 were studied at room temperature. Circular dichroism (CD) of the complexes have been investigated.

  16. Coordination Polymers Derived from Non-Steroidal Anti-Inflammatory Drugs for Cell Imaging and Drug Delivery.

    PubMed

    Paul, Mithun; Dastidar, Parthasarathi

    2016-01-18

    A new series of Mn(II) coordination polymers, namely, [{Mn(L)(H2 O)2 }⋅2 Nap]∞ (CP1), [{Mn(L)(Ibu)2 (H2 O)2 }]∞ (CP2), [{Mn(L)(Flr)2 (H2 O)2 }]∞ (CP3), [{Mn(L)(Ind)2 (H2 O)2 }⋅H2 O]∞ (CP4), [{Mn2 (L)2 (μ-Flu)4 (H2 O)}⋅L]∞ (CP5), [{Mn2 (L)2 (μ-Tol)4 (H2 O)2 }]∞ (CP6) and [{Mn2 (L)2 (μ-Mef)4 (H2 O)2 }]∞ (CP7) (Nap=naproxen, Ibu=ibuprofen, Flr=flurbiprofen, Ind=indometacin, Flu=flufenamic acid, Tol=tolfenamic acid and Mef=mefenamic acid) derived from various non-steroidal anti-inflammatory drugs (NSAIDs) and the organic linker 1,2-bis(4-pyridyl)ethylene (L) have been synthesized with the aim of being used for cell imaging and drug delivery. Single-crystal X-ray diffraction (SXRD) studies revealed that the NSAID molecules were part of the coordination polymeric network either through coordination to the metal center (in the majority of the cases) or through hydrogen bonding. Remarkably, all the Mn(II) coordination polymers were found to be soluble in DMSO, thereby making them particularly suitable for the desired biological applications. Two of the coordination polymers (namely, CP1 and CP3) reported herein, were found to be photoluminescent both in the solid as well as in the solution state. Subsequent experiments (namely, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), and PGE2 (prostaglandin E2 ) assays) established their biocompatibility and anti-inflammatory response. In vitro studies by using a macrophage cell line (i.e., RAW 264.7) revealed that both CP1 and CP3 were excellent cell imaging agents. Finally, biodegradability studies under simulated physiological conditions in phosphate-buffered saline (PBS) at pH 7.6 showed that slow and sustained release of the corresponding NSAID was indeed possible from both CP1 and CP3.

  17. Metal coordination polymers of 2,3-bis(benzimidazol-1-ylmethyl)quinoxaline: Syntheses, crystal structures and luminescent properties

    NASA Astrophysics Data System (ADS)

    Du, Jian-Long; Wei, Zi-Zhang; Hu, Tong-Liang

    2011-06-01

    Two new metal-organic frameworks, {[Cu LI]·CHCl 3} ∞( 1) and {[Hg L(Br) 2] 4·2CH 2Cl 2} ∞ ( 2) have been prepared by reacting CuI and HgBr 2 with the new flexible ligand L [ L = 2,3-Bis(benzimidazol-1-ylmethyl)quinoxaline]. Both complexes have been characterized by elemental analysis, IR, TGA, XRPD, and single crystal X-ray diffraction determination. In 1, the Cu(I) ion takes tetrahedral coordination geometry, and the flexible ligands bridge dinuclear units (Cu 2I 2) to form a one dimensional (1D) double chain structure. While in 2, the Hg(II) coordinates to two bromine ions and two nitrogen donors of L to form a 1D coordination polymer. The structure differences of the two complexes mainly depend on the geometry of the metal ions and the influence of anions. The coordination features of the ligand have also been primarily investigated by density functional theory (DFT) calculations. In addition, the fluorescent properties of the complexes and free ligand L have been investigated in the solid state at room temperature.

  18. Synthesis, structure, and luminescence property of a series of Ag-Ln coordination polymers with the N-heterocyclic carboxylato ligand

    NASA Astrophysics Data System (ADS)

    Jin, Jing; Chen, Chong; Gao, Yan; Zhao, Ran; Wang, Xiuyan; Lü, Chunxin; Chi, Yuxian; Niu, Shuyun

    2016-03-01

    Six Ln-Ag coordination polymers {[LnAg2(IN)4(H2O)5]·NO3·2H2O}n (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg2(IN)4(H2O)2]·NO3·H2O}n (3), [LnAg(pdc)2]n (Ln=Eu(4) and Pr (5), H2pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc)2(H2O)4]n (6) (H2bidc=benzimidazole-5,6-dicarboxylic acid) have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV-vis-NIR absorption spectra, fluorescence spectra and thermogravimetric analysis. Structural analyses reveal that the six polymers exhibit 0D (polymer (1)), 1D (polymer (2)), 2D (polymers (3) and (5)) and 3D (polymers (4) and (6)) infinite structures, respectively. Polymers (1)-(6) exhibit the Ln(III) characteristic emission in the near-infrared (NIR) region or in the visible region. Especially, the NIR emission bands of polymers 1, 5 and 6 evidently present shift or splitting due to formation of the Ln-Ag coordination polymers. This can be attributed to the tune of inner levels in Ln-Ag system caused by the interact and influence between the 4d orbital of the Ag(I) ion and the 4f orbital of the Ln(III) ion, which can be confirmed by the UV-vis-NIR absorption spectra of the polymers. In addition, the distortion of coordination geometry as well as difference of the coordination number around the Ag(I) ion affect the structure framework.

  19. Tri- and tetra-substituted cyclen based lanthanide(III) ion complexes as ribonuclease mimics: a study into the effect of log Ka, hydration and hydrophobicity on phosphodiester hydrolysis of the RNA-model 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP).

    PubMed

    Fanning, Ann-Marie; Plush, Sally E; Gunnlaugsson, Thorfinnur

    2015-05-28

    A series of tetra-substituted 'pseudo' dipeptide ligands of cyclen (1,4,7,10,-tetraazacyclododecane) and a tri-substituted 3'-pyridine ligand of cyclen, and the corresponding lanthanide(III) complexes were synthesised and characterised as metallo-ribonuclease mimics. All complexes were shown to promote hydrolysis of the phosphodiester bond of 2-hydroxypropyl-4-nitrophenyl phosphate (HPNP, τ1/2 = 5.87 × 10(3) h), a well known RNA mimic. The La(III) and Eu(III) tri-substituted 3'-pyridine lanthanide(III) complexes being the most efficient in promoting such hydrolysis at pH 7.4 and at 37 °C; with τ1/2 = 1.67 h for La(III) and 1.74 h for Eu(III). The series was developed to provide the opportunity to investigate the consequences of altering the lanthanide(III) ion, coordination ability and hydrophobicity of a metallo-cavity on the rate of hydrolysis using the model phosphodiester, HPNP, at 37 °C. To further provide information on the role that the log Ka of the metal bound water plays in phosphodiester hydrolysis the protonation constants and the metal ion stability constants of both a tri and tetra-substituted 3'pyridine complex were determined. Our results highlighted several key features for the design of lanthanide(III) ribonucelase mimics; the presence of two metal bound water molecules are vital for pH dependent rate constants for Eu(III) complexes, optimal pH activity approximating physiological pH (∼7.4) may be achieved if the log Ka values for both MLOH and ML(OH)2 species occur in this region, small changes to hydrophobicity within the metallo cavity influence the rate of hydrolysis greatly and an amide adjacent to the metal ion capable of forming hydrogen bonds with the substrate is required for achieving fast hydrolysis.

  20. Rare configuration of tautomeric benzimidazolecarboxylate ligands in cadmium(II) and copper(II) coordination polymers

    SciTech Connect

    Wu, Jing-Yun; Yang, Ciao-Wei; Chen, Hui-Fang; Jao, Yu-Chen; Huang, Sheng-Ming; Tsai, Chiitang; Tseng, Tien-Wen; Lee, Gene-Hsiang; Peng, Shie-Ming; Lu, Kuang-Lieh

    2011-07-15

    Two Cd(HBimc)-based isomers, [Cd(HBimc{sup N})(HBimc{sup T})(H{sub 2}O)].3.5H{sub 2}O.EtOH (1a.3.5H{sub 2}O.EtOH, H{sub 2}Bimc=1H-benzimidazole-5-carboxylic acid) and [Cd(HBimc{sup N})(HBimc{sup T})(H{sub 2}O)] (1b), and two Cu(HMBimc)-based coordination polymers, [Cu(HMBimc{sup N}){sub 2}(H{sub 2}O)].1/2H{sub 2}O (2.1/2H{sub 2}O, H{sub 2}MBimc=2-methyl-1H-benzimidazole-5-carboxylic acid) and [Cu(HMBimc{sup T}){sub 2}].2THF.H{sub 2}O (3.2THF.H{sub 2}O), were self-assembled from Cd(ClO{sub 4}){sub 2}.6H{sub 2}O/H{sub 2}Bimc and Cu(ClO{sub 4}){sub 2}.6H{sub 2}O/H{sub 2}MBimc systems, respectively. Compound 1a adopts a ladder-like chain structure, comprised of a hydrogen-bond-stabilized Cd{sub 2}(HBimc{sup N}){sub 2}-metallocyclic stair and a 1D straight -(Cd-HBimc{sup T}){sub n}- edge, whereas compound 1b exhibits a 2D (4,4)-rhombus layered structure, intercrossed by 1D -(Cd-HBimc{sup N}){sub n}- chains and -(Cd-HBimc{sup T}){sub n}- chains. Compound 2 shows a 1D double-stranded wave-like chain from two single-stranded wave-like -(Cu-HMBimc{sup N}){sub n}- chains and compound 3 adopts a 2D (4,4)-topological layer structure, intercrossed by subunits of 1D -(Cu-HMBimc{sup T}){sub n}- chains. Interestingly, a pair of tautomeric HBimc building blocks-normal (N or HBimc{sup N}) and tautomer (T or HBimc{sup T})-is simultaneously included in the structures of 1a and 1b, whilst the N- and T-configured HMBimc building blocks are present as separate entities in Cu species, 2 and 3, respectively. The existence of only a tautomer (T) mode of the benzimidazolecarboxylate-based ligand in a Cu(II) network is observed for the first time. - Graphical abstract: A pair of tautomeric HBimc building blocks (normal (N) and tautomer (T)) is found simultaneously in two Cd(II) networks, whereas, the normal and tautomer modes of HMBimc are present as separate entities in two Cu(II) frameworks. The isolation of a Cu(II) network with only a tautomer (T) mode of the benzimidazolecarboxylate

  1. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

    NASA Astrophysics Data System (ADS)

    He, Tian; Yue, Ke-Fen; Zhao, Yi-xing; Chen, San-Ping; Zhou, Chun-sheng; Yan, Ni

    2016-07-01

    Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H2O}n (1), {[Zn(bib)(atbip)]·H2O}n (2), [Zn(bib)(2,2‧-tda)]}n (3) and {[Zn(bib)(5-tbipa)]·EtOH}n (4), (H2atibdc=5-amino-2,4,6-triiodoisophthalic acid, H2atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2‧-H2tad=2,2‧-thiodiacetic acid, 5-H2tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1-4. The fluorescent properties of complexes 1-4 were studied. In addition, the thermal decompositions properties of 1-4 were investigated by simultaneous TG/DTG-DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1-4 are calculated by the integral Kissinger's method and Ozawa-Doyle's method. The activation energy E (E1=209.658 kJ·mol-1, E2=250.037 kJ mol-1, E3=225.300 kJ mol-1, E4=186.529 kJ·mol-1) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH‡, ΔG‡ and ΔS‡) at the peak temperatures of the DTG curves were also calculated. ΔG‡>0 indicates that the skeleton collapse is not spontaneous. ΔHd>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The structural stability could be illustrated from the point of thermodynamics and kinetics. Their thermal decompositions properties of 1-4 were

  2. A two-dimensional π-d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour.

    PubMed

    Huang, Xing; Sheng, Peng; Tu, Zeyi; Zhang, Fengjiao; Wang, Junhua; Geng, Hua; Zou, Ye; Di, Chong-an; Yi, Yuanping; Sun, Yimeng; Xu, Wei; Zhu, Daoben

    2015-06-15

    Currently, studies on organic two-dimensional (2D) materials with special optic-electronic properties are attracting great research interest. However, 2D organic systems possessing promising electrical transport properties are still rare. Here a highly crystalline thin film of a copper coordination polymer, Cu-BHT (BHT=benzenehexathiol), is prepared via a liquid-liquid interface reaction between BHT/dichloromethane and copper(II) nitrate/H2O. The morphology and structure characterization reveal that this film is piled up by nanosheets of 2D lattice of [Cu3(C6S6)]n, which is further verified by quantum simulation. Four-probe measurements show that the room temperature conductivity of this material can reach up to 1,580 S cm(-1), which is the highest value ever reported for coordination polymers. Meanwhile, it displays ambipolar charge transport behaviour and extremely high electron and hole mobilities (99 cm(2 )V(-1 )s(-1) for holes and 116 cm(2 )V(-1 )s(-1) for electrons) under field-effect modulation.

  3. Structural diversification and photocatalytic properties of three Cd(II) coordination polymers decorated with different auxiliary ligands

    NASA Astrophysics Data System (ADS)

    Yin, Wen-Yu; Zhuang, Guo-Yong; Huang, Zuo-Long; Cheng, Hong-Jian; Zhou, Li; Ma, Man-Hong; Wang, Hao; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin

    2016-03-01

    Three cadmium coordination polymers, [Cd(bismip)]n (1), {[Cd(bismip)(phen)]·H2O}n (2) and {[Cd2(bismip)2(4,4‧-bipy)]·2H2O}n (3) (H2bismip=5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid, phen=1,10-phenanthroline, 4,4‧-bipy=4,4‧-bipyridine) have been prepared under solvothermal conditions. In 1, the [Cd4(bismip)3] units are jointed by bismip ligands to afford a three-dimensional (3D) architecture. Complex 2 exhibits a 3D supramolecular framework based on the interconnection of 1D chains through hydrogen bonding interactions and π-π packing interactions. 3 is a two-fold interpenetrating 3D architecture with a (4·82)(42·84) Schläfli symbol in which 2D layers are interlinked by 4,4‧-bipy ligands. The diverse structures of compounds 1-3 indicate that the auxiliary ligands have significant effects on the final structures. The photoluminescent properties and photocatalytic properties of these coordination polymers in the solid state were also investigated. Remarkably, 3 shows the wide gap semiconductor nature and exhibit excellent photocatalytic performance.

  4. Catenation control in the two-dimensional coordination polymers based on tritopic carboxylate linkers and azamacrocyclic nickel(II) complexes.

    PubMed

    Lampeka, Yaroslaw D; Tsymbal, Liudmyla V; Barna, Andrij V; Shuĺga, Yulija L; Shova, Sergiu; Arion, Vladimir B

    2012-04-14

    Four new coordination polymer frameworks, namely [(NiL(1))(3)(BTB)(2)]·6H(2)O, [(NiL(2))(3)(BTB)(2)]·6H(2)O, [(NiL(3))(3)(BTB)(2)]·6H(2)O and [(NiL(2))(3)(BTC)(2)]·10.25H(2)O (L(1) = 1,4,8,11-tetraazacyclotetradecane, L(2) = 3-methyl-1,3,5,8,12-pentaazacyclotetradecane, L(3) = 3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane, BTC(3-) = benzene-1,3,5-tricarboxylate, BTB(3-) = 4,4',4''-benzene-1,3,5-triyl-tribenzoate) were prepared in water-N,N-dimethylformamide solutions. The molecular and crystal structures of these compounds are compared to the related coordination polymers formed by nickel(II) macrocyclic cations to examine the effect of carboxylate linker size on the framework architecture. Luminescent properties of the complexes based on the BTB(3-) bridging ligand are also discussed. PMID:22266979

  5. Syntheses, structures, and photoluminescence of three-dimensional lanthanide coordination polymers with 2,5-pyridinedicarboxylic acid

    SciTech Connect

    Huang Yan; Song Yishan; Yan, Bing Shao Min

    2008-08-15

    Four new open-framework coordination polymers of lanthanide 2,5-pyridinedicarboxylates, with the formulas Pr2(pydc){sub 3}(H{sub 2}O){sub 2} (1), Ln(pydc)(Hpydc) (Ln=Tb (2), Er (3), Eu (5)), and Gd(pydc)(nic)(H{sub 2}O) (4) (H{sub 2}pydc=2,5-pyridinedicarboxylic acid, Hnic=nicotinic acid), have been hydrothermally synthesized and four of them (except Eu (5)) have been structurally characterized. Complex 1 consists of two types of ligand-binding modes contributing to link the PrO{sub 7}N(H{sub 2}O) polyhedral chains to three-dimensional (3D) open-framework architecture. Complexes 2 and 3 are isostructural and feature unique 3D cage-like supramolecular frameworks remarkably different from that of 1, owing to the different ligand-bridging pattern. Complex 4, however, has the distinct 3D open-framework architecture due to the presence of unexpected nicotinate ligands, which may be derived from pydc ligands via in-situ decarboxylation under the hydrothermal condition. - Graphical abstract: Four new lanthanide coordination polymers have been hydrothermally synthesized by the reaction of 2,5-pyridinedicarboxylic acid with the corresponding lanthanide nitrates, and they show three types of 3D open-framework architecture. Complexes 2 and 5 show strong characteristic green (or red) luminescence and long lifetimes.

  6. Syntheses, crystal structure and properties of two novel coordination polymers with the flexible tetrazole-1-acetic acid (Htza)

    SciTech Connect

    Dong Wenwen; Zhao Jun; Xu Li

    2008-05-15

    Two new coordination polymers, [Ag(tza)]{sub {infinity}} (1) (Htza=tetrazole-1-acetic acid) and [Cu(tza){sub 2}]{sub {infinity}} (2) have been prepared at room temperature and characterized by X-ray crystallography, IR, UV-vis, fluorescence spectra and magnetism analysis. Compound 1 exhibits extended helical chains through bridging ligand tza. The Ag{center_dot}{center_dot}{center_dot}Ag interactions between the adjacent chains form a 3-D framework featuring the extended tza-connected Ag chains that obviously affect the photoluminescent property. Compound 2 features undulated layered structure with hourglass-shaped [Cu{sub 4}(tza){sub 4}] as subunits with the weak ferromagnetic interactions between Cu(II) ions, which are further stabilized by inter-lamellar C-H{center_dot}{center_dot}{center_dot}O hydrogen bonds in the resulting 3-D supramolecular framework. - Graphical abstract: Two novel coordination polymers, [Ag(tza)]{sub {infinity}} (1) and [Cu(tza){sub 2{infinity}} (2) have been prepared and characterized. Compound 1 features extended double-stranded helical chains. Compound 2 features undulated layered structure with hourglass-shaped [Cu{sub 4}(tza){sub 4}] as subunits with the weak ferromagnetic interactions between Cu(II) ions.

  7. 3-D coordination polymers based on the tetrathiafulvalenetetracarboxylate (TTF-TC) derivative: synthesis, characterization, and oxidation issues.

    PubMed

    Nguyen, Thi Le Anh; Demir-Cakan, Rezan; Devic, Thomas; Morcrette, Mathieu; Ahnfeldt, Tim; Auban-Senzier, Pascale; Stock, Norbert; Goncalves, Anne-Marie; Filinchuk, Yaroslav; Tarascon, Jean-Marie; Férey, Gérard

    2010-08-01

    The reactivity of the redox-active tetracarboxylic acid derived from the tetrathiafulvalene (TTF-TC)H(4) with alkaline cations (K, Rb, Cs) is reported. The exploration of various experimental parameters (temperature, pH) led to the formation of four crystalline three-dimensional coordination polymers formulated M(2)(TTF-TC)H(2) (M = K, Rb, Cs), denoted MIL-132(K), MIL-133(isostructural K, Rb), and MIL-134(Cs). Thermogravimetric analysis and thermodiffraction show that all of the solids are thermally stable up to 150-200 degrees C in the air. In order to exploit the possibility of oxidation of the organic linker in TTF-based compounds, they were employed as positive electrodes in a classical lithium cell. A highly reversible cyclability was achieved at high current density (10 C) with a reasonable performance (approximately 50 mAh g(-1)). Finally, combined electro-(sub)hydrothermal synthesis was used to prepare a fifth 3-D coordination polymer formulated K(TTF-TC)H(2) (denoted MIL-135(K)), this time not based on the neutral TTF-TC linker but its radical, oxidized form TTF-TC(+*). This solid is less thermally stable than its neutral counterparts but exhibits a semiconducting behavior, with a conductivity at room temperature of about 1 mS cm(-1).

  8. Syntheses and structures of three heterometallic coordination polymers derived from 4-pyridin-3-yl-benzoic acid

    NASA Astrophysics Data System (ADS)

    Fang, Wei-Hui; Yang, Guo-Yu

    2014-04-01

    Three lanthanide-transition-metal coordination polymers, namely, [Er2L6(H2O)][Cu2I2] (1), [ErL3][CuI] (2), and [Dy2L6(BPDC)0.5(H2O)4][Cu3I2] (3) (HL=4-pyridin-3-yl-benzoic acid, H2BPDC=4,4‧-biphenyldicarboxylic acid) have been made by reacting Ln2O3 and CuI with HL at different temperatures under hydrothermal conditions. All the complexes are characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction, respectively. 1-3 all construct from dimeric {Ln2} and {Cu2} units and exhibit two types of the structural features: 1 is a two-dimensional layer, 2-3 are three-dimensional frameworks. Interestingly, the in situ formation of the BPDC ligand is found in the structure of 3. The distinct architectures of these complexes indicated that the reaction temperature plays an important role in the formation of higher dimensional coordination polymers.

  9. A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour

    PubMed Central

    Huang, Xing; Sheng, Peng; Tu, Zeyi; Zhang, Fengjiao; Wang, Junhua; Geng, Hua; Zou, Ye; Di, Chong-an; Yi, Yuanping; Sun, Yimeng; Xu, Wei; Zhu, Daoben

    2015-01-01

    Currently, studies on organic two-dimensional (2D) materials with special optic-electronic properties are attracting great research interest. However, 2D organic systems possessing promising electrical transport properties are still rare. Here a highly crystalline thin film of a copper coordination polymer, Cu-BHT (BHT=benzenehexathiol), is prepared via a liquid–liquid interface reaction between BHT/dichloromethane and copper(II) nitrate/H2O. The morphology and structure characterization reveal that this film is piled up by nanosheets of 2D lattice of [Cu3(C6S6)]n, which is further verified by quantum simulation. Four-probe measurements show that the room temperature conductivity of this material can reach up to 1,580 S cm−1, which is the highest value ever reported for coordination polymers. Meanwhile, it displays ambipolar charge transport behaviour and extremely high electron and hole mobilities (99 cm2 V−1 s−1 for holes and 116 cm2 V−1 s−1 for electrons) under field-effect modulation. PMID:26074272

  10. Luminescent zinc terephthalate coordination polymers with pyridylnicotinamide ligands: Effect of added base and nitrogen donor disposition on topology

    NASA Astrophysics Data System (ADS)

    Goldsworthy, Jessica S.; Staples, Richard J.; LaDuca, Robert L.

    2014-03-01

    Hydrothermal reaction of zinc nitrate, potassium terephthalate (K2tere), and 3-pyridylnicotinamide (3-pna) or 4-pyridylnicotinamide (4-pna) afforded coordination polymers with different dimensionality depending on nitrogen donor disposition and the initial pH of the reaction mixture. {[Zn(tere)(3-pna)2(H2O)2]ṡ2H2O}n (1) was prepared in the presence of aqueous NaOH, and manifests 1-D coordination polymer chains with monodentate 3-pna ligands. A mixture of {[Zn(tere)(3-pna)]ṡ3H2O}n (2) and {[Zn4(tere)3(OH)2(3-pna)2]ṡ2H2O}n (3) was prepared by performing a similar reaction in the absence of extra base. Compound 2 shows a 2-D (6,3) hexagonal grid topology with very tight interdigitation, while 3 has a 2-fold interpenetrated 3-D pcu network built from {Zn4(OCO)2(OH)2} centrosymmetric tetrameric nodes. {[Zn(tere)(4-pna)]ṡH2O}n (4) has parallel 2-fold interpenetrated sawtooth layer motifs. Luminescent and thermal decomposition properties are also discussed.

  11. A two-dimensional π-d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour

    NASA Astrophysics Data System (ADS)

    Huang, Xing; Sheng, Peng; Tu, Zeyi; Zhang, Fengjiao; Wang, Junhua; Geng, Hua; Zou, Ye; di, Chong-An; Yi, Yuanping; Sun, Yimeng; Xu, Wei; Zhu, Daoben

    2015-06-01

    Currently, studies on organic two-dimensional (2D) materials with special optic-electronic properties are attracting great research interest. However, 2D organic systems possessing promising electrical transport properties are still rare. Here a highly crystalline thin film of a copper coordination polymer, Cu-BHT (BHT=benzenehexathiol), is prepared via a liquid-liquid interface reaction between BHT/dichloromethane and copper(II) nitrate/H2O. The morphology and structure characterization reveal that this film is piled up by nanosheets of 2D lattice of [Cu3(C6S6)]n, which is further verified by quantum simulation. Four-probe measurements show that the room temperature conductivity of this material can reach up to 1,580 S cm-1, which is the highest value ever reported for coordination polymers. Meanwhile, it displays ambipolar charge transport behaviour and extremely high electron and hole mobilities (99 cm2 V-1 s-1 for holes and 116 cm2 V-1 s-1 for electrons) under field-effect modulation.

  12. Stepwise assembly of a semiconducting coordination polymer [Cd8S(SPh)14(DMF)(bpy)]n and its photodegradation of organic dyes.

    PubMed

    Xu, Chao; Hedin, Niklas; Shi, Hua-Tian; Xin, ZhiFeng; Zhang, Qian-Feng

    2015-04-14

    Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4'-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4'-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

  13. Lanthanide coordination polymers based on multi-donor ligand containing pyridine and phthalate moieties: Structures, luminescence and magnetic properties

    SciTech Connect

    Feng, Xun; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Qiang Shi, Zhi; Wu, Xu-Hong; Ng, Seik-Weng

    2013-10-15

    A new family of five lanthanide-organic coordination polymers incorporating multi-functional N-hetrocyclic dicarboxylate ligand, namely, [Ln{sub 2}(Hdpp){sub 2}(dpp){sub 2}]{sub n}Ln=Pr(1), Eu(2), Gd(3), Dy(4), Er(5) (H{sub 2}dpp=1-(3, 4-dicarboxyphenyl) pyridin-4-ol) have been fabricated successfully through solvothermal reaction of 1-(3,4-dicarboxyphenyl)-4-hydroxypyridin-1-ium chloride with trivalent lanthanide salts, and have been characterized systematically. The complexes 1–5 are isomorphous and isostructural. They all feature three dimensional (3D) frameworks based on the interconnection of 1D double chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 4+} basic carboxylate as secondary building unit (SBU). The results of magnetic analysis shows the same bridging fashion of carboxylic group in this case results in the different magnetic properties occurring within lanthanide polymers. Moreover, the Eu(III) and Dy(III) complexes display characteristic luminescence emission in the visible regions. - Graphical abstract: A new family of lanthanide-organic frameworks incorporating multi-donor twisted ligand has been fabricated successfully, and has been characterized systematically. The complexes 1–5 are isostructural, and all feather three dimensional (3D) frameworks based on the interconnection of 1D double stride chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 2+} basic carboxylate as secondary building unit (SBU). Display Omitted - Highlights: • New family of lanthanide–organic coordination polymers incorporating multifunctional N-hetrocyclic dicarboxylate ligand has been fabricated. • They have been characterized systematically. • They all feather three dimensional frameworks based on the binuclear moiety of [Ln{sub 2}(Hdpp){sub 2}]{sup 2+}. • The Eu(III) and Dy(III) analogues exhibit intense photoluminescence.

  14. Copper(II)-lanthanide(III) coordination polymers constructed from pyridine-2,5-dicarboxylic acid: Preparation, crystal structure and photoluminescence

    SciTech Connect

    Xia Zhengqiang; Wei Qing; Chen Sanping; Feng Xinming; Xie Gang; Qiao Chengfang; Zhang Guochun; Gao Shengli

    2013-01-15

    A series of 3d-4f heterometallic coordination polymers, formulated as {l_brace} [Cu{sub 3}Ln{sub 2}(pydc){sub 6}(H{sub 2}O){sub 12}]{center_dot}4H{sub 2}O{r_brace} {sub n} [Ln=Tb (1), Eu (2), Dy (3), Ho (4), Lu (5)], {l_brace} [CuNd{sub 2}(pydc){sub 4}(H{sub 2}O){sub 3}]{center_dot}H{sub 2}O{r_brace} {sub n} (6) and {l_brace} [Cu{sub 3}Pr{sub 2}(pydc){sub 6}(H{sub 2}O){sub 13}]{center_dot}4H{sub 2}O{r_brace} {sub n} (7) (where H{sub 2}pydc=pyridine-2,5-dicarboxylic acid), have been hydrothermally prepared by reactions of H{sub 2}pydc ligand with lanthanide ions in the presence of Cu(II) ion. X-ray crystal structure analysis reveals that these compounds exhibit rich structural chemistry. 1-5 are isomorphous and present a two-dimensional network constructed from Ln{sub 2}Cu{sub 2}L{sub 2}(H{sub 2}O){sub 2} SBU rings and CuL{sub 2}(H{sub 2}O) building blocks. In 6, two-dimensional ladder-like layers based on Nd(III) belts and CuL{sub 2}O{sub 2} units are assembled by H{sub 2}pydc ligands into a three-dimensional open framework. Polymer 7 displays a two-dimensional wave-like layer structure containing two distinct ring units, in which a new coordination mode of the pydc{sup 2-} ligand is observed. The results indicate that the coordination flexibility of the pydc{sup 2-} ligand and lanthanide contraction effect play cooperative roles in the formation of coordination polymers with different polymeric architectures. Compounds 1-2 exhibit intense green and red luminescence emission characteristics of Tb(III) and Eu(III), respectively. Furthermore, elemental analyses (EA), infrared spectra (IR) and thermogravimetric analyses (TGA) of these compounds were also studied. - Graphical abstract: Seven 3d-4f heterometallic coordination polymers were synthesized by reactions of H{sub 2}pydc with lanthanide metal ions in the presence of Cu{sup 2+}, the effects of Cu{sup 2+} on the structures and photoluminescent properties of Ln-pydc{sup 2-} systems were investigated. Highlights

  15. Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

    PubMed

    Díaz-Gallifa, Pau; Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2014-06-16

    Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges. PMID:24901707

  16. Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

    PubMed

    Díaz-Gallifa, Pau; Fabelo, Oscar; Pasán, Jorge; Cañadillas-Delgado, Laura; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

    2014-06-16

    Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network. Heterometallic chains formed by the regular alternation of two nine-coordinate lanthanide(III) polyhedra [Ln(III)O9] and one compressed cobalt(II) octahedron [Co(II)O6] along the crystallographic c-axis are cross-linked by bta ligands within each layer of 3-6. Magnetic susceptibility measurements on polycrystalline samples for 3-6 have been carried out in the temperature range of 2.0-300 K. The magnetic behavior of these types of Ln(III)-Co(II) complexes, which have been modeled by using matrix dagonalization techniques, reveals the lack of magnetic coupling for 3 and 4, and the occurrence of weak antiferromagnetic interactions within the Gd(III)-Gd(III) (5) and Tb(III)-Tb(III) (6) dinuclear units through the exchange pathway provided by the double oxo(carboxylate) and double syn-syn carboxylate bridges.

  17. Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries.

    PubMed

    Malliakas, Christos D; Leung, Kevin; Pupek, Krzysztof Z; Shkrob, Ilya A; Abraham, Daniel P

    2016-04-28

    Fluorinated carbonates are pursued as liquid electrolyte solvents for high-voltage Li-ion batteries. Here we report aggregation of [Li(+)(FEC)3]n polymer species in fluoroethylene carbonate containing electrolytes and scrutinize the causes for this behavior. PMID:27040896

  18. Two new pyridine-2,3-dicarboxylate coordination polymers prepared from zerovalent metal precursor: Syntheses, luminescent and magnetic properties

    NASA Astrophysics Data System (ADS)

    Semerci, Fatih; Yeşilel, Okan Zafer; Soylu, Mustafa Serkan; Yerli, Yusuf; Dal, Hakan

    2014-02-01

    Two new K+/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), {K2[Cu(μ-pydc)2]·3H2O}n (1) and {[Zn(μ-pydc)(H2O)(4-mim)]·H2O}n (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. In the sandwiched 3D anionic framework of 1, pydc ligands exhibit hexadentate coordination; tridentate coordination bond with Cu(II) and tridentate ionic interaction with K+ ions. {K2[Cu(μ-pydc)2]·3H2O}n shows a rare topology consists of three dimensional (3,4,5)-connected network with the point symbol of {42.6}2{42.84}{43.6.86}2. The distorted square pyramidal geometry of 2 is completed with an nitrogen atom from 4-mim and aqua ligand to form a 1D polynuclear structure. The hydrogen bonds link the 1D chains into 3D architecture. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature.

  19. Two 2D silver(I) coordination polymers derived from mixed ligands: Syntheses, structures, photoluminescent and thermal properties

    NASA Astrophysics Data System (ADS)

    Liu, Fu-Jing; Sun, Di; Li, Yun-Hua; Hao, Hong-Jun; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-07-01

    Two isomers of the aminobenzonitrile were reacted with Ag 2O and phthalic acid under ultrasonic condition, yielding two coordination polymers (CPs) of the formula [Ag 2( o-abn)(pa)] n ( 1) and [Ag 4( m-abn)(pa) 2] n ( 2). They have been characterized by elemental analysis, IR spectrum and single crystal X-ray diffraction. Both complexes 1 and 2 are 2D sheet structures which contain two different Ag(I) aggregates, 1D silver helical chain and 2D silver sheet for 1 and 2, respectively. The o-abn in 1 adopts a rare tridentate μ 3- N, N' N' mode to bridge the neighboring 1D silver chains to form a 2D coordination network, while the m-abn ligand just acts as a monodentate N-donor in 2 and does not contribute to the extension of the 2D silver sheet to the higher dimensionality. As the change of the relative position of amino and cyano groups of the aminobenzonitrile ligand, the dimensionality of the Ag(I) aggregates in 1 and 2 increases from 1D to 2D, which indicates that the relative positions of amino and cyano groups of aminobenzonitrile play an important role in the formation of the diverse Ag(I) aggregates, as a consequence, different 2D coordination networks are produced. Additionally, results about emissive behaviors and thermal stabilities of them are discussed.

  20. REDV/Rapamycin-loaded polymer combinations as a coordinated strategy to enhance endothelial cells selectivity for a stent system.

    PubMed

    Wei, Yu; Zhang, Jing-xun; Ji, Ying; Ji, Jian

    2015-12-01

    A major challenge in the development of drug eluting stent platform is the sustained inhibition of smooth muscle cell (SMC) proliferation while endothelial cell (EC) coverage is promoted. We demonstrated in this study that the combination of rapamycin-loaded polymer base layer and Arg-Glu-Asp-Val (REDV) peptide tethered top layer is a coordinated strategy to enhance EC-specific selectivity. A 2-methacryloyloxyethyl phosphorylcholine(MPC)-co-n-stearyl methacrylate (SMA) [PMS] film was prepared as a base coating to load rapamycin. MPC-co-SMA-co-p-nitrophenyloxycarbonyl polyethyleneglycol methacrylate (MEONP) [PMSN] was synthesized to form the top layer, which conjugated the EC-specific ligand REDV peptide that promotes EC attachment. The top layer functioned as a diffusion barrier, and the polymer film can sustain the rapamycin release of for over 120 days. The In vitro cell behavior of EC and SMC indicated that the rapamycin loaded polymer film inhibited cell growth in the first few days of drug release. After 8 days of drug release, the composite coating consistently resisted the nonspecific adsorption of SMC, whereas REDV enhanced EC attachment specifically. A rabbit iliac injury model was used to evaluate the in vivo of the application of this kind of surface-modified stainless steel stent. The composite polymer coating approach could significantly promote re-endothelialization without causing neointimal hyperplasia. The combination of an EC-specific ligand with rapamycin-loaded polymeric coating may potentially be an effective therapeutic alternative to improve currently available drug-eluting stents. PMID:26613858

  1. REDV/Rapamycin-loaded polymer combinations as a coordinated strategy to enhance endothelial cells selectivity for a stent system.

    PubMed

    Wei, Yu; Zhang, Jing-xun; Ji, Ying; Ji, Jian

    2015-12-01

    A major challenge in the development of drug eluting stent platform is the sustained inhibition of smooth muscle cell (SMC) proliferation while endothelial cell (EC) coverage is promoted. We demonstrated in this study that the combination of rapamycin-loaded polymer base layer and Arg-Glu-Asp-Val (REDV) peptide tethered top layer is a coordinated strategy to enhance EC-specific selectivity. A 2-methacryloyloxyethyl phosphorylcholine(MPC)-co-n-stearyl methacrylate (SMA) [PMS] film was prepared as a base coating to load rapamycin. MPC-co-SMA-co-p-nitrophenyloxycarbonyl polyethyleneglycol methacrylate (MEONP) [PMSN] was synthesized to form the top layer, which conjugated the EC-specific ligand REDV peptide that promotes EC attachment. The top layer functioned as a diffusion barrier, and the polymer film can sustain the rapamycin release of for over 120 days. The In vitro cell behavior of EC and SMC indicated that the rapamycin loaded polymer film inhibited cell growth in the first few days of drug release. After 8 days of drug release, the composite coating consistently resisted the nonspecific adsorption of SMC, whereas REDV enhanced EC attachment specifically. A rabbit iliac injury model was used to evaluate the in vivo of the application of this kind of surface-modified stainless steel stent. The composite polymer coating approach could significantly promote re-endothelialization without causing neointimal hyperplasia. The combination of an EC-specific ligand with rapamycin-loaded polymeric coating may potentially be an effective therapeutic alternative to improve currently available drug-eluting stents.

  2. Robust Photocatalytic H2O2 Production by Octahedral Cd3(C3N3S3)2 Coordination Polymer under Visible Light

    PubMed Central

    Zhuang, Huaqiang; Yang, Lifang; Xu, Jie; Li, Fuying; Zhang, Zizhong; Lin, Huaxiang; Long, Jinlin; Wang, Xuxu

    2015-01-01

    Herein, we reported a octahedral Cd3(C3N3S3)2 coordination polymer as a new noble metal-free photocatalyst for robust photocatalytic H2O2 production from methanol/water solution. The coordination polymer can give an unprecedented H2O2 yield of ca. 110.0 mmol • L−1 • g−1 at pH = 2.8 under visible light illumination. The characterization results clearly revealed that the photocatalytic H2O2 production proceeds by a pathway of two-electron reduction of O2 on the catalyst surface. This work showed the potential perspective of Mx(C3N3S3)y (M = transitional metals) coordination polymers as a series of new materials for solar energy storage and conversion. PMID:26582652

  3. Fabrication of Ag/CPs composite material, an effective strategy to improve the photocatalytic performance of coordination polymers under visible irradiation.

    PubMed

    Xu, Xinxin; Cui, Zhongping; Qi, Ji; Liu, Xiaoxia

    2013-10-01

    To enhance the photocatalytic property of coordination polymers (CPs) in the visible light region, Ag loaded coordination polymer composite materials (Ag/CPs) were synthesized successfully through a photoreduction reaction of Ag(+) on the surface of CPs. Photoluminescence (PL) was used to investigate the separation of photogenerated electron-hole pairs and the results illustrated Ag/CPs display higher quantum yields than CPs. This can be attributed to the strong interactions between Ag nanorods and coordination polymers, which lead to electron-hole pair separation between Ag nanorods and CPs. The degradation of Rhodamine B (RhB) was investigated to study the photocatalytic activities. Ag/CPs exhibited excellent photocatalytic activity in the UV and visible light region, while CPs can only decompose RhB under the irradiation of UV light. Furthermore, Ag/CPs showed outstanding stability during degradation of RhB.

  4. Synthesis of Biocompatible Nanoparticulate Coordination Polymers for Diagnostic and Therapeutic Applications

    NASA Astrophysics Data System (ADS)

    Kandanapitiye, Murthi S.

    The combination of nanotechnology with medicinal chemistry has developed into a burgeoning research area. Nanomaterials (NMs) could be seamlessly interfaced with various facets in biology, biochemistry, medicinal chemistry and environmental chemistry that may not be available to the same material in the bulk scale. This dissertation research has focused on the development of nanoparticulate coordination polymers for diagnostic and therapeutic applications. Modern imaging techniques include X-ray computed tomography (CT), magnetic resonance imaging (MRI), single photon emission computed tomography (SPECT) and positron emission tomography (PET). We have successfully developed several types of nanoparticulate diagnostics and therapeutics that have some potential usefulness in biomedicine. Synthesis and characterization of nanoparticulate based PET (Positron emission tomography)/SPECT (Single photon emission computed tomography) are discussed in chapter 3. In chapter 4, preparation and potential utility of non-gadolinium based MRI contrast agent are reported for T1-weighted application. As far as the solely effectiveness of relaxation is concerned, Gd-based T 1-weighted MRI contrast agents have excellent enhancement of image contrast but they have risks of biological toxicity. Consequently, the search for T 1-weighted CAs with high efficacy and low toxicity has gained attention toward the Mn(II) and Fe(III). Fe(III) is considered to be more toxic to cells because free ferric or ferrous ions can catalyze the production of reactive oxygen species via the Fenton reactions. Paramagnetic chelates of Mn(II) could be employed as T1-weighted CAs. However, it is challenging to design and synthesize highly stable Mn(II) complexes that could maintain the integrity when administered to living system. Chapter 4 describes the synthesis and utility of nanoparticulate Mn analogue of Prussian blue (K2Mn 3[FeII(CN)6]2) as an effective T1 MRI contrast agent for cellular imaging X

  5. From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd(II) using (113)Cd solid-state NMR.

    PubMed

    Frost, Jamie M; Kobera, Libor; Pialat, Amélie; Zhang, Yixin; Southern, Scott A; Gabidullin, Bulat; Bryce, David L; Murugesu, Muralee

    2016-08-23

    Studies of three related Cd(II) systems (a discrete [Cd(II)2] unit, a one-dimensional [Cd(II)2]n coordination polymer and a Cd(II)-based MOF) all derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of (113)Cd-(113)Cd J coupling in the polymer that is detectable by solid-state NMR ((2)JCd-Cd = ∼65 Hz). PMID:27507123

  6. From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd(II) using (113)Cd solid-state NMR.

    PubMed

    Frost, Jamie M; Kobera, Libor; Pialat, Amélie; Zhang, Yixin; Southern, Scott A; Gabidullin, Bulat; Bryce, David L; Murugesu, Muralee

    2016-08-23

    Studies of three related Cd(II) systems (a discrete [Cd(II)2] unit, a one-dimensional [Cd(II)2]n coordination polymer and a Cd(II)-based MOF) all derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of (113)Cd-(113)Cd J coupling in the polymer that is detectable by solid-state NMR ((2)JCd-Cd = ∼65 Hz).

  7. Novel 1D coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n}: Synthesis, structure, magnetic properties and thermal behavior

    SciTech Connect

    Fomina, Irina; Dobrokhotova, Zhanna; Aleksandrov, Grygory; Emelina, Anna; Bykov, Mikhail; Bogomyakov, Artem; Puntus, Lada; Novotortsev, Vladimir; Eremenko, Igor

    2012-01-15

    The new 1D coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n} (1), where Piv=OOCBu{sup t-}, was synthesized in high yield (>95%) by the reaction of thulium acetate with pivalic acid in air at 100 Degree-Sign S. According to the X-ray diffraction data, the metal atoms in compound 1 are in an octahedral ligand environment unusual for lanthanides. The magnetic and luminescence properties of polymer 1, it's the solid-phase thermal decomposition in air and under argon, and the thermal behavior in the temperature range of -50 Horizontal-Ellipsis +50 Degree-Sign S were investigated. The vaporization process of complex 1 was studied by the Knudsen effusion method combined with mass-spectrometric analysis of the gas-phase composition in the temperature range of 570-680 K. - Graphical Abstract: Novel 1D coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n} was synthesized and studied by X-ray diffraction. The magnetic, luminescence properties, the thermal behavior and the volatility for the compound {l_brace}Tm(Piv){sub 3{r_brace}n} were investigated. Black-Small-Square Highlights: Black-Right-Pointing-Pointer We synthesized the coordination polymer {l_brace}Tm(Piv){sub 3{r_brace}n}. Black-Right-Pointing-Pointer Tm atoms in polymer have the coordination number 6. Black-Right-Pointing-Pointer Polymer exhibits blue-color emission at room temperature. Black-Right-Pointing-Pointer Polymer shows high thermal stability and volatility. Black-Right-Pointing-Pointer Polymer has no phase transitions in the range of -50 Horizontal-Ellipsis +50 Degree-Sign S.

  8. Gas adsorption/separation properties of metal directed self-assembly of two coordination polymers with 5-nitroisophthalate

    SciTech Connect

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Keskin, Seda; Şahin, Onur

    2014-02-15

    Two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Thermal properties of the complexes showed that both complexes were stable over 320 °C. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. - Graphical abstract: In this study, two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. Display Omitted - Highlights: • Two new coordination polymers with 5-nitroisophthalate and 1,2-bis(4-pyridyl)ethane. • Atomically detailed simulation studies of the complexes. • Complex 2 can be proposed as molecular sieve to separate CO{sub 2} from CH{sub 4} at low pressures.

  9. The structures and luminescence properties of lanthanide (Ln = Sm, Eu and Tb) metal-organic coordination polymers based on 5-(2-hydroxyethoxy)isophthalate ligand

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Zhang, Yu-Jie; Qin, Jie; Chen, Yong; Zhao, Ying

    2015-03-01

    Three unreported isomorphous Ln-containing metal-organic coordination polymeric complexes {LnL(HL)ṡ(H2O)2}n (Ln = Sm (1), Eu (2) and Tb (3), CCDC 971815-971817) were synthesized based on 5-(2-hydroxyethoxy) isophthalic acid (H2L) under hydrothermal conditions. The obtained coordination polymers were characterized by IR, elemental analysis, thermal analysis and X-ray diffraction In solid state, these polymers featured 3-D supramolecular structures constructed by 2-D sheets through H-bonds. Investigation of photoluminescence properties of H2L and 1-3 showed all of them exhibited intense fluorescent emissions in the solid state at room temperature.

  10. Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2

    DOEpatents

    Matzger, Adam J.; Liu, Baojian; Wong-Foy, Antek G.

    2016-07-19

    Flowing supercritical CO.sub.2 is used to activate metal organic framework materials (MOF). MOFs are activated directly from N,N-dimethylformamide (DMF) thus avoiding exchange with a volatile solvent. Most MCPs display increased surface areas directly after treatment although those with coordinatively unsaturated metal centers benefit from additional heating.

  11. Six Zn(II) and Cd(II) coordination polymers assembled from a similar binuclear building unit: tunable structures and luminescence properties.

    PubMed

    Zhang, Liyan; Rong, Lulu; Hu, Guoli; Jin, Suo; Jia, Wei-Guo; Liu, Ji; Yuan, Guozan

    2015-04-21

    Six Zn(ii) and Cd(ii) coordination polymers were constructed by treating a 2-substituted 8-hydroxyquinolinate ligand containing a pyridyl group with zinc or cadmium salts, and characterized by a variety of techniques. Interestingly, based on a similar binuclear Zn(ii) or Cd(ii) building unit, the supramolecular structures of the six coordination polymers () exhibit an unprecedented structural diversification due to the different choices of metal salts. and represent a novel 2D framework containing 1D infinite right- and left-handed helical chains. and are 2D coordination frameworks based on binuclear Cd(ii) building units. For and , the L ligands can bridge binuclear building units forming a 1D infinite chain. Interestingly, the adjacent Cd2O2 planes of the 1D chain in are in parallel with each other, while the dihedral angle between the two Zn2O2 planes in is 83.43°. Photoluminescence properties revealed that the six coordination polymers exhibit redshifted emission maximum compared with the free ligand HL, which can be ascribed to an increased conformational rigidity and the fabrication of coplanar binuclear building units M2L2 in . Coordination polymers also display distinct fluorescence lifetimes and quantum yields because of their different metal centers and supramolecular structures.

  12. Structural diversity and magnetic properties of six metal-organic coordination polymers based on semi-rigid V-shape tetracarboxylic acid ligand

    NASA Astrophysics Data System (ADS)

    Yang, Shanshan; Bai, Yue-Ling; Xing, Feifei; Zhao, Yongmei; Li, Ming-Xing; Shao, Min; Zhu, Shourong

    2016-04-01

    Six Mn metal-organic frameworks have been synthesized under solvothermal conditions with V-shaped terphenyl tetracarboxylate ligands (H4ttac). Their structures were characterized by elemental analysis, infrared spectra, PXRD, thermogravimetric analysis, and single-crystal X-ray diffraction analysis. Crystal structures reveal that the coordination number of H4ttac ligand varies from 6 to 10, and each ligand links 4-8 Mn(II) ions. Coordination modes vary from η6μ4 to η10μ8. The existence of DMF solvent can increase coordination number of the ligand. The first coordination saturated phthalate is presented. The variable-temperature magnetic studies indicate that complexes exhibit dominant antiferromagnetic behaviors. Structural parameters and coordination modes were summarized. The porosity of these complexes is less than 15%, indicating that the V-shape ligand is not a good choice to construct porous coordination polymers.

  13. Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

    SciTech Connect

    Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen; Ma, Lu-Fang; Wang, Li-Ya

    2014-12-15

    Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H{sub 2}O)]){sub n} (1), ([Co(4-Nbdc)(bpp) (H{sub 2}O)]){sub n} (2), ([Ni(4-Nbdc)(bpp)(H{sub 2}O)]·H{sub 2}O){sub n} (3), and ([Mn{sub 2}(3-Nbdc){sub 2}(bib){sub 3}]·2H{sub 2}O){sub n} (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal–carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (6{sup 6}) dia topology and (4{sup 4}.6{sup 10}.8)(4{sup 4}.6{sup 2}) fsc topology, and both of them contain metal–carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)–carboxylate binuclear in 1 (J=1.27 cm{sup −1}) and Ni(II)–carboxylate chain in 3 (J=1.44 cm{sup −1}), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)–carboxylate chain in 4 (J=−0.77 cm{sup −1}). - Highlights: • Four novel coordination polymers were hydrothermally synthesized. • 1 is 1D quasi-trapezoidal chain and 2 is brick-wall layer both with dinuclear units. • 3 and 4 show 3D frameworks both with 1D metal–carboxylate chains. • 1 and 3 exhibit ferromagnetic coupling, while 4 shows antiferromagnetic coupling.

  14. Mixed ligand coordination polymers with flexible bis-imidazole linker and angular sulfonyldibenzoate: Crystal structure, photoluminescence and photocatalytic activity

    SciTech Connect

    Bisht, Kamal Kumar; Rachuri, Yadagiri; Parmar, Bhavesh; Suresh, Eringathodi

    2014-05-01

    Four ternary coordination polymers (CPs) namely, ([Ni(SDB)(BITMB)(H{sub 2}O)]·H{sub 2}O){sub n} (CP1), ([Cd(SDB)(BITMB) (H{sub 2}O)]·(THF)(H{sub 2}O)){sub n} (CP2), ([Zn{sub 2}(SDB){sub 2}(BITMB)]·(THF){sub 2}){sub n} (CP3) and ([Co{sub 2}(SDB){sub 2}(BITMB)]·(Dioxane){sub 3}){sub n} (CP4) composed of angular dicarboxylate SDB (4,4'-sulfonyldibenzoate) and N-donor BITMB (1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethyl benzene) have been synthesized by solvothermal reactions and characterized by single crystal X-ray diffraction and other physico-chemical techniques. CP1 possesses one-dimensional ribbon type metal–organic motifs glued together by H-bonds and π⋯π interactions, whereas CP2–CP4, exhibit non-interpenetrated sql networks supported by weak supramolecular interactions. Structural diversity of these CPs can be attributed to the coordination geometry adopted by the metal nodes, versatile coordination modes of SDB and conformational flexibility of BITMB. Solid state luminescence properties of CP1–CP4 were explored. Photocatalytic performance of all CPs for the decomposition of metanil yellow by dilute hydrogen peroxide in the presence of visible light was also investigated. 25–83% dye removal from aqueous solutions in the presence of CP1–CP4 was observed. - Graphical abstract: Four new ternary transition metal CPs have been hydrothermally prepared and their structural aspects as well as photocatalytic activity for decolourization of metanil yellow (MY) dye have been investigated. - Highlights: • Four ternary coordination polymers containing Ni, Cd, Zn and Co center are prepared. • Crystal structure and thermal stability of all four CPs has been described. • PL and diffuse reflectance spectra of synthesized CPs have also been examined. • Band gap values suggest semiconducting behavior of prepared CPs. • Photocatalytic activity of CPs for oxidative degradation of metanil yellow is studied.

  15. Cobalt oxide 2D nano-assemblies from infinite coordination polymer precursors mediated by a multidentate pyridyl ligand.

    PubMed

    Li, Guo-Rong; Xie, Chen-Chao; Shen, Zhu-Rui; Chang, Ze; Bu, Xian-He

    2016-05-01

    In this work, the construction of Co3O4 two dimensional (2D) nano-assemblies utilizing infinite coordination polymers (ICPs) as precursors was investigated, aiming at the morphology targeted fabrication and utilization of 2D materials. Based on the successful modulation of morphology, a rose-like Co based ICP precursor was obtained, which was further transformed into porous Co3O4 nanoflake assemblies with a well-preserved 2D morphology and a large surface area. The mechanism of the morphology modulation was illustrated by systematic investigation, which demonstrated the crucial role of a modulating agent in the formation of 2D nano-assemblies. In addition, the cobalt oxide 2D nano-assemblies are fabricated into a lithium anode combined with graphene, and the remarkable capacity and stability (900 mA h g(-1) after 50 cycles) of the resulting Co3O4/G nanocomposite indicates its potential in lithium battery applications. PMID:27064264

  16. Sonochemical synthesis of two new nano lead(II) coordination polymers: Evaluation of structural transformation via mechanochemical approach.

    PubMed

    Aboutorabi, Leila; Morsali, Ali

    2016-09-01

    Two new lead(II) mixed-ligand coordination polymers, [Pb(PNO)(SCN)]n (1) and [Pb(PNO)(N3)]n (2), (HPNO=picolinic acid N-oxide) were synthesized by a sonochemical method and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analysis. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction. The thermal behavior of 1 and 2 were studied by thermal gravimetric analysis. Structural transformations of compounds 1 and 2 were evaluated through anion-replacement processes by mechanochemical method. Moreover, the effect of sonication conditions including time, concentrations of initial reagents and power of irradiation were evaluated on size and morphology of compounds 1 and 2.

  17. Cobalt oxide 2D nano-assemblies from infinite coordination polymer precursors mediated by a multidentate pyridyl ligand.

    PubMed

    Li, Guo-Rong; Xie, Chen-Chao; Shen, Zhu-Rui; Chang, Ze; Bu, Xian-He

    2016-05-01

    In this work, the construction of Co3O4 two dimensional (2D) nano-assemblies utilizing infinite coordination polymers (ICPs) as precursors was investigated, aiming at the morphology targeted fabrication and utilization of 2D materials. Based on the successful modulation of morphology, a rose-like Co based ICP precursor was obtained, which was further transformed into porous Co3O4 nanoflake assemblies with a well-preserved 2D morphology and a large surface area. The mechanism of the morphology modulation was illustrated by systematic investigation, which demonstrated the crucial role of a modulating agent in the formation of 2D nano-assemblies. In addition, the cobalt oxide 2D nano-assemblies are fabricated into a lithium anode combined with graphene, and the remarkable capacity and stability (900 mA h g(-1) after 50 cycles) of the resulting Co3O4/G nanocomposite indicates its potential in lithium battery applications.

  18. Effects of different factors on the formation of nanorods and nanosheets of silver(I) coordination polymer

    NASA Astrophysics Data System (ADS)

    Shahangi Shirazi, Fatemeh; Akhbari, Kamran; Kawata, Satoshi; Ishikawa, Ryuta

    2016-11-01

    In order to evaluation the effects of solvent, concentration of initial reagents and ultrasonic irradiations on formation different morphologies of [Ag2(pta)(H2O)]n (1), [H2pta = phthalic acid], nanostructures, we design some experiments and synthesized six sample of 1 under different conditions. nanorods and nanosheets of a silver(I) coordination polymer, were synthesized under these conditions. These nanostructures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. If we arrange the order of these three factors upon their importance in formation compound 1 nanostructures, first we can select the type of solvent as the effective factor, then the concentration of initial reagents and finally the existence of ultrasonic irradiation which can change the morphology of 1 in low concentration of initial reagents. Thermal stability of these six samples was also studied by thermo gravimetric (TG) and differential thermal analyses (DTA).

  19. Simulation of mesogenic diruthenium tetracarboxylates: Development of a force field for coordination polymers of the MMX type.

    PubMed

    Castro, Maria Ana; Roitberg, Adrian E; Cukiernik, Fabio D

    2013-06-01

    A classical molecular mechanics force field, able to simulate coordination polymers (CP) based on ruthenium carboxylates (Ru2 (O2CReq )4 Lax) (eq = equatorial group containing aliphatic chains, Lax = axial ligand), has been developed. New parameters extracted from experimental data and quantum calculations on short aliphatic chains model systems were included in the generalized AMBER force field. The proposed parametrization was evaluated using model systems with known structure, containing either short or long aliphatic chains; experimental results were reproduced satisfactorily. This modified force field, although in a preliminary stage, could then be applied to long chain liquid crystalline compounds. The resulting atomistic simulations allowed assessing the relative influence of the factors determining the CP conformation, determinant for the physical properties of these materials. PMID:23436725

  20. Photochemical Reduction of Low Concentrations of CO2 in a Porous Coordination Polymer with a Ruthenium(II)-CO Complex.

    PubMed

    Kajiwara, Takashi; Fujii, Machiko; Tsujimoto, Masahiko; Kobayashi, Katsuaki; Higuchi, Masakazu; Tanaka, Koji; Kitagawa, Susumu

    2016-02-18

    Direct use of low pressures of CO2 as a C1 source without concentration from gas mixtures is of great interest from an energy-saving viewpoint. Porous heterogeneous catalysts containing both adsorption and catalytically active sites are promising candidates for such applications. Here, we report a porous coordination polymer (PCP)-based catalyst, PCP-Ru(II) composite, bearing a Ru(II) -CO complex active for CO2 reduction. The PCP-Ru(II) composite showed improved CO2 adsorption behavior at ambient temperature. In the photochemical reduction of CO2 the PCP-Ru(II) composite produced CO, HCOOH, and H2 . Catalytic activity was comparable with the corresponding homogeneous Ru(II) catalyst and ranks among the highest of known PCP-based catalysts. Furthermore, catalytic activity was maintained even under a 5 % CO2 /Ar gas mixture, revealing a synergistic effect between the adsorption and catalytically active sites within the PCP-Ru(II) composite.

  1. Six new coordination polymers constructed by 3-carboxyl-5-oxycarboxymethylpyridinio-1-carboxylate: Crystal structures, topologies, photoluminescent and magnetic properties

    SciTech Connect

    Yuan, Hong-Yan; Han, Min-Min; Jiang, Xian-Rong; Jiang, Zhan-Guo; Feng, Yun-Long

    2013-06-01

    Six new two-dimensional (2D) coordination polymers, [ML(H₂O)₃]ₙ (M=Zn (1), Cd (2), Mn (3), Co (4)), [CdL(H₂O)]ₙ} (5), [CdL(4,4´-bipy)]ₙ·nH₂O (6), (H₂L=3-carboxyl-5-oxycarboxymethylpyridinio-1-carboxylate, 4,4´-bipy=4,4´-bipyridine), have been hydrothermally synthesized and characterized by single crystal X-ray diffraction analyses, IR spectra, and thermogravimetric analyses. 1, 2, 3, 4 are isostructural and feature a binodal (4,6)-connected topology with left- and right-handed helical chains with a pitch of 9.9560 Å. 5 can be topologically presented as an uninodal 6-connected network if the hydrogen bonds are also considered. 6 is a binodal (3,5)-connected 2D layer network. The photoluminescent properties of 1, 2, 5, 6 and magnetic properties of 3, 4 have been studied and discussed. - Graphical abstract: The structural differences show that the ligand, the metal center, and the reaction conditions have great influence on the structure of the final assembly. Highlights: • A new asymmetric flexible tricarboxylate ligand of 3-carboxyl-5-oxycarboxymethylpyridinio-1-carboxylate was synthesized. • Six new two-dimensional (2D) coordination polymers have been hydrothermally obtained. • 1, 2, 3, 4 are isostructural and feature a binodal (4,6)-connected topology with left- and right-handed helical chains. • The photoluminescent properties of 1, 2, 5, 6 and magnetic properties of 3, 4 have been studied.

  2. Construction of magnet-type coordination polymers using high-spin {Ni4}-citrate cubane as secondary building units.

    PubMed

    Li, Teng; Wang, Yanyan; Qin, Lei; Han, Tian; Ding, You-Song; Hu, Yue-Qiao; Zheng, Yan-Zhen

    2016-06-28

    Three potassium(i)-nickel(ii)-citrate coordination polymers, [K4Ni6(cit)4(H2O)8]n (), [K14Ni17(cit)12(H2O)33]n·10nH2O () and [K8Ni12(cit)8(H2O)15]n·2nH2O (), have been self-assembled in a solvothermal synthesis. Interestingly, these three polymers share the common {Ni4(cit)4}(8-) cubane ({Ni4}-cit-cub) secondary building units. The diverse ways of linking the {Ni4}-cit-cubs and additional isolated octahedral Ni(ii) ions lead to disparate magnetic exchange-coupling interactions, namely ferromagnetic for and and antiferromagnetic for . More importantly, the weak ferromagnetic interactions do not lead to long-range magnetic ordering above 2 K in or , whereas the strong antiferromagnetic interaction in leads to uncompensated magnetic moment due to the non-collinear alignment of the spins. Further magnetic characterization confirms the coexistence of spin-canted antiferromagnetism and spin glass behaviour in . PMID:27294693

  3. Reversible Guest Binding in a Non-Porous Fe(II) Coordination Polymer Host Toggles Spin Crossover.

    PubMed

    Lennartson, Anders; Southon, Peter; Sciortino, Natasha F; Kepert, Cameron J; Frandsen, Cathrine; Mørup, Steen; Piligkos, Stergios; McKenzie, Christine J

    2015-11-01

    Formation of either a dimetallic compound or a 1 D coordination polymer of adiponitrile adducts of [Fe(bpte)](2+) (bpte=[1,2-bis(pyridin-2-ylmethyl)thio]ethane) can be controlled by the choice of counteranion. The iron(II) atoms of the bis(adiponitrile)-bridged dimeric complex [Fe2 (bpte)2 (μ2 -(NC(CH2 )4 CN)2 ](SbF6 )4 (2) are low spin at room temperature, as are those in the polymeric adiponitrile-linked acetone solvate polymer {[Fe(bpte)(μ2 -NC(CH2 )4 CN)](BPh4 )2 ⋅Me2 CO} (3⋅Me2 CO). On heating 3⋅Me2 CO to 80 °C, the acetone is abruptly removed with an accompanying purple to dull lavender colour change corresponding to a conversion to a high-spin compound. Cooling reveals that the desolvate 3 shows hysteretic and abrupt spin crossover (SCO) S=0↔S=2 behaviour centred at 205 K. Non-porous 3 can reversibly absorb one equivalent of acetone per iron centre to regenerate the same crystalline phase of 3⋅Me2 CO concurrently reinstating a low-spin state. PMID:26394897

  4. Towards Acid-Tolerated Ethanol Dehydration: Chitosan-Based Mixed Matrix Membranes Containing Cyano-Bridged Coordination Polymer Nanoparticles.

    PubMed

    Wu, C-W; Kang, Chao-Hsiang; Lin, Yi-Feng; Tung, Kuo-Lun; Deng, Yu-Heng; Ahamad, Tansir; Alshehri, Saad M; Suzuki, Norihiro; Yamauchi, Yusuke

    2016-04-01

    Prussian blue (PB) nanoparticles, one of many cyano-bridged coordination polymers, are successfully incorporated into chitosan (CS) polymer to prepare PB/CS mixed matrix membranes (MMMs). The PB nanoparticles are uniformly distributed in the MMMs without the collapse of the original PB structure. As-prepared PB/CS MMMs are used for ethanol dehydration at 25 °C in the pervaporation process. The effect of loading PB in CS matrix on pervaporation performance is carefully investigated. The PB/CS membrane with 30 wt% PB loading shows the best performance with a permeate flux of 614 g. m-2 . h-1 and a separation factor of 1472. The pervaporation using our PB/CS membranes exhibits outstanding performance in comparison with the previously reported CS-based membranes and MMMs. Furthermore, the addition of PB allows PB/CS MMMs to be tolerant of acidic environment. The present work demonstrates good pervaporation performance of PB/CS MMMs for the separation of an ethanol/water (90:10 in wt%) solution. Our new system provides an opportunity for dehydration of bioethanol in the future. PMID:27451778

  5. Towards Acid-Tolerated Ethanol Dehydration: Chitosan-Based Mixed Matrix Membranes Containing Cyano-Bridged Coordination Polymer Nanoparticles.

    PubMed

    Wu, C-W; Kang, Chao-Hsiang; Lin, Yi-Feng; Tung, Kuo-Lun; Deng, Yu-Heng; Ahamad, Tansir; Alshehri, Saad M; Suzuki, Norihiro; Yamauchi, Yusuke

    2016-04-01

    Prussian blue (PB) nanoparticles, one of many cyano-bridged coordination polymers, are successfully incorporated into chitosan (CS) polymer to prepare PB/CS mixed matrix membranes (MMMs). The PB nanoparticles are uniformly distributed in the MMMs without the collapse of the original PB structure. As-prepared PB/CS MMMs are used for ethanol dehydration at 25 °C in the pervaporation process. The effect of loading PB in CS matrix on pervaporation performance is carefully investigated. The PB/CS membrane with 30 wt% PB loading shows the best performance with a permeate flux of 614 g. m-2 . h-1 and a separation factor of 1472. The pervaporation using our PB/CS membranes exhibits outstanding performance in comparison with the previously reported CS-based membranes and MMMs. Furthermore, the addition of PB allows PB/CS MMMs to be tolerant of acidic environment. The present work demonstrates good pervaporation performance of PB/CS MMMs for the separation of an ethanol/water (90:10 in wt%) solution. Our new system provides an opportunity for dehydration of bioethanol in the future.

  6. Prototypes of Lanthanide(III) Agents Responsive to Enzymatic Activities in Three Complementary Imaging Modalities: Visible/Near-Infrared Luminescence, PARACEST-, and T1-MRI.

    PubMed

    He, Jiefang; Bonnet, Célia S; Eliseeva, Svetlana V; Lacerda, Sara; Chauvin, Thomas; Retailleau, Pascal; Szeremeta, Frederic; Badet, Bernard; Petoud, Stéphane; Tóth, Éva; Durand, Philippe

    2016-03-01

    We report first prototypes of responsive lanthanide(III) complexes that can be monitored independently in three complementary imaging modalities. Through the appropriate choice of lanthanide(III) cations, the same reactive ligand can be used to form complexes providing detection by (i) visible (Tb(3+)) and near-infrared (Yb(3+)) luminescence, (ii) PARACEST- (Tb(3+), Yb(3+)), or (iii) T1-weighted (Gd(3+)) MRI. The use of lanthanide(III) ions of different natures for these imaging modalities induces only a minor change in the structure of complexes that are therefore expected to have a single biodistribution and cytotoxicity.

  7. Deconvolution of the role of metal and pH in metal coordinating polymers

    NASA Astrophysics Data System (ADS)

    Cazzell, Seth; Holten-Andersen, Niels

    Nature uses metal binding amino acids to engineer both mechanical properties and structural functionality. Some examples of this metal binding behavior can be found in both mussel foot protein and DNA binding protein. The mussel byssal thread contains reversible intermolecular protein-metal bonds, allowing it to withstand harsh intertidal environments. Zinc fingers form intramolecular protein-metal bonds to stabilize the tertiary structure of DNA binding proteins, allowing specific structural functionality. Inspired by both these metal-binding materials, we present mechanical and spectroscopic characterization of a model polymer system, designed to mimic this bonding. Through these studies, we are able to answer fundamental polymer physics questions, such as the role of pH and metal to ligand ratio, illuminating both the macroscopic and microscopic material behavior. These understandings further bio-inspired engineering techniques that are used to design viscoelastic soft materials. I was supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

  8. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven self-assembly and host/guest interactions.

    PubMed

    Yan, Xuzhou; Cook, Timothy R; Pollock, J Bryant; Wei, Peifa; Zhang, Yanyan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2014-03-26

    An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal-ligand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel-sol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained. PMID:24621148

  9. High Anodic Performance of Co 1,3,5-Benzenetricarboxylate Coordination Polymers for Li-Ion Battery.

    PubMed

    Li, Chao; Lou, Xiaobing; Shen, Ming; Hu, Xiaoshi; Guo, Zhi; Wang, Yong; Hu, Bingwen; Chen, Qun

    2016-06-22

    We report the designed synthesis of Co 1,3,5-benzenetricarboxylate coordination polymers (CPs) via a straightforward hydrothermal method, in which three kinds of reaction solvents are selected to form CPs with various morphologies and dimensions. When tested as anode materials in Li-ion battery, the cycling stabilities of the three CoBTC CPs at a current density of 100 mA g(-1) have not evident difference; however, the reversible capacities are widely divergent when the current density is increased to 2 A g(-1). The optimized product CoBTC-EtOH maintains a reversible capacity of 473 mAh g(-1) at a rate of 2 A g(-1) after 500 galvanostatic charging/discharging cycles while retaining a nearly 100% Coulombic efficiency. The hollow microspherical morphology, accessible specific area, and the absence of coordination solvent of CoBTC-EtOH might be responsible for such difference. Furthermore, the ex situ soft X-ray absorption spectroscopy studies of CoBTC-EtOH under different states-of-charge suggest that the Co ions remain in the Co(2+) state during the charging/discharging process. Therefore, Li ions are inserted to the organic moiety (including the carboxylate groups and the benzene ring) of CoBTC without the direct engagement of Co ions during electrochemical cycling.

  10. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven self-assembly and host/guest interactions.

    PubMed

    Yan, Xuzhou; Cook, Timothy R; Pollock, J Bryant; Wei, Peifa; Zhang, Yanyan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2014-03-26

    An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal-ligand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel-sol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained.

  11. Structural and spectral properties of a zinc(II) coordination polymer: a combined experimental and theoretical study.

    PubMed

    Hao, Jin-Ming; Li, Guang-Yue; Li, Yue-Hua; Cui, Guang Hua

    2014-10-15

    A novel 1D zinc(II) coordination polymer [Zn(bbbm)Cl2]n (where bbbm=1,4-bis(N-benzimidazolyl)butane) was synthetized by ZnCl2 and bbbm ligand under hydrothermal conditions, and its structural and spectral properties were studied by both experimental and theoretical techniques. The center zinc(II) ion displays four-coordinated in a tetrahedral geometry by two chloride anions and two N atoms of distinct bbbm ligands. Adjacent chains are further connected into a 2D layer structure through π-π stacking interactions. Vibrational frequencies of [Zn(bbbm)Cl2]n have been calculated using DFT/B3LYP/TZVP method, and well reproduced IR data. Furthermore, the vertical excitation energies from time-dependent DFT calculation confirmed that the fluorescent peaks at 385nm and 450nm could respectively be assigned to the π→π(*) transition within the bbbm ligands and π→n transition from chloride anion to bbbm ligand.

  12. Reversible Single-Crystal to Single-Crystal Transformations of a Zn(II)-Salicyaldimine Coordination Polymer Accompanying Changes in Coordination Sphere and Network Dimensionality upon Dehydration and Rehydration.

    PubMed

    Wu, Jing-Yun; Chang, Ching-Yun; Tsai, Chi-Jou; Lee, Jey-Jau

    2015-11-16

    A fluorescent Zn(II)-salicyaldimine coordination polymer, [Zn(L(salpyca))(H2O)]n (1; H2L(salpyca) = 4-hydroxy-3-(((pyridin-2-yl)methylimino)methyl)benzoic acid), showing a one-dimensional (1D) zigzag chain structure has been hydro(solvo)thermally synthesized. Removal of coordination water molecules in 1 by thermal dehydration gives rise to the dehydration product [Zn(L(salpyca))]n (1'), which has a dizinc-based two-dimensional (2D) gridlike (4,4)-layer structure. X-ray powder diffraction (XRPD) patterns, thermogravimetric (TG) analyses, and infrared (IR) spectra all clearly indicate that the structure of 1 is quite flexible as a result of a reversible 1D-2D single-crystal to single-crystal (SCSC) transformation upon removal and rebinding of coordination water molecules, which accompanies changes in coordination sphere and network dimensionality. Additionally, Zn(II)-salicyaldimine polymers 1 and 1' exhibit different solid-state photoluminescences at 458 and 480 nm, respectively. This is reasonably attributed to the close-packing effect and/or the influences of the differences on the conformation and the coordination mode of the L(salpyca) ligand and the coordination geometry around the Zn(II) center.

  13. Derivation and Testing of Explicit Equations of Motion for Polymers Described by Internal Coordinates

    NASA Astrophysics Data System (ADS)

    Mazur, A. K.; Dorofeev, V. E.; Abagyan, R. A.

    1991-02-01

    General Lagrange's equations of motion for a system of polymeric molecules are obtained in an explicit form. They can be used for simulating molecular dynamics of large molecules. The molecular conformations are described by internal coordinates, i.e., bond lengths, valence angles, and torsion angles. The equations derived permit any internal degrees of freedom to be frozen. The method is applied to an oligopeptide in an α-helical conformation. Three models of the molecule with different degrees of fixation are compared. It is shown that the method permits one to increase significantly the time step in molecular dynamics calculations.

  14. The coating of conducting copolymer on coordination polymer nanorod: A visible light active p-n heterojunction photocatalyst for H2 production

    NASA Astrophysics Data System (ADS)

    Jia, Yuan; Mei, Ming-liang; Xu, Xin-xin; Wang, Lin-shan

    2016-06-01

    A visible light active p-n heterojunction photocatalyst was synthesized successfully through in-situ chemical oxidation copolymerization of aniline (ANI) and diphenylamine-4-sulfonate (DPAS) with the existence of coordination polymer nanorod (CPNR) under initiation of ammonium persulfate (APS). Compared with neat coordination polymer nanorod, the resulted p-n heterojunction photocatalyst exhibits higher H2 generationrate under visible light irradiation. In this heterojunction photocatalyst, as a p-type semiconductor possessing suitable energy levels with coordination polymer nanorod, poly-(aniline-co-N-(4-sulfophenyl)-aniline) (PAPSA) forms p-n heterojunction with n-type coordination polymer nanorod, the inner electric field of p-n heterojunction accelerates the separation of electrons and holes, which enhances H2 production performance. Furthermore, the influence of concentration ratio between DPAS and ANI on photocatalytic property of the p-n heterojunction photocatalyst was discussed and a reasonable condition to fabricate photocatalyst with high H2 generationrate had been obtained. During photocatalytic water splitting H2 generation, the p-n heterojunction photocatalyst exhibited outstanding stability.

  15. Multifunctional Magnetic Gd(3+) -Based Coordination Polymer Nanoparticles: Combination of Magnetic Resonance and Multispectral Optoacoustic Detections for Tumor-Targeted Imaging in vivo.

    PubMed

    An, Qiao; Liu, Jing; Yu, Meng; Wan, Jiaxun; Li, Dian; Wang, Changchun; Chen, Chunying; Guo, Jia

    2015-11-11

    To overcome traditional barriers in optical imaging and microscopy, optoacoustic-imaging has been changed to combine the accuracy of spectroscopy with the depth resolution of ultrasound, achieving a novel modality with powerful in vivo imaging. However, magnetic resonance imaging provides better spatial and anatomical resolution. Thus, a single hybrid nanoprobe that allows for simultaneous multimodal imaging is significant not only for cutting edge research in imaging science, but also for accurate clinical diagnosis. A core-shell-structured coordination polymer composite microsphere has been designed for in vivo multimodality imaging. It consists of a Fe3 O4 nanocluster core, a carbon sandwiched layer, and a carbocyanine-Gd(III) (Cy-Gd(III) ) coordination polymer outer shell (Fe3 O4 @C@Cy-Gd(III) ). Folic acid-conjugated poly(ethylene glycol) chains are embedded within the coordination polymer shell to achieve extended circulation and targeted delivery of probe particles in vivo. Control of Fe3 O4 core grain sizes results in optimal r2 relaxivity (224.5 × 10(-3) m(-1) s(-1) ) for T2 -weighted magnetic resonance imaging. Cy-Gd(III) coordination polymers are also regulated to obtain a maximum 25.1% of Cy ligands and 5.2% of Gd(III) ions for near-infrared fluorescence and T1 -weighted magnetic resonance imaging, respectively. The results demonstrate their impressive abilities for targeted, multimodal, and reliable imaging.

  16. Water molecule-driven reversible single-crystal to single-crystal transformation of a multi-metallic coordination polymer with controllable metal ion movement.

    PubMed

    Niu, Zheng; Ma, Jian-Gong; Shi, Wei; Cheng, Peng

    2014-02-21

    A single-crystal to single-crystal (SC-SC) transformation process driven by water molecules has been exhibited by a multi-metallic coordination polymer. The in situ heating single crystal X-ray diffraction technique was applied to study the control of metal ion movement in the reversible SC-SC transformation process.

  17. Highly selective CO2 adsorption accompanied with low-energy regeneration in a two-dimensional Cu(II) porous coordination polymer with inorganic fluorinated PF6(-) anions.

    PubMed

    Noro, Shin-ichiro; Hijikata, Yuh; Inukai, Munehiro; Fukushima, Tomohiro; Horike, Satoshi; Higuchi, Masakazu; Kitagawa, Susumu; Akutagawa, Tomoyuki; Nakamura, Takayoshi

    2013-01-01

    High selectivity and low-energy regeneration for adsorption of CO(2) gas were achieved concurrently in a two-dimensional Cu(II) porous coordination polymer, [Cu(PF(6))(2)(4,4'-bpy)(2)](n) (4,4'-bpy = 4,4'-bipyridine), containing inorganic fluorinated PF(6)(-) anions that can act as moderate interaction sites for CO(2) molecules.

  18. Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

    NASA Astrophysics Data System (ADS)

    Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen; Ma, Lu-Fang; Wang, Li-Ya

    2014-12-01

    Four new coordination polymers {[Ni(4-Nbdc)(bpa)(H2O)]}n (1), {[Co(4-Nbdc)(bpp) (H2O)]}n (2), {[Ni(4-Nbdc)(bpp)(H2O)]·H2O}n (3), and {[Mn2(3-Nbdc)2(bib)3]·2H2O}n (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal-carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (66) dia topology and (44.610.8)(44.62) fsc topology, and both of them contain metal-carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)-carboxylate binuclear in 1 (J=1.27 cm-1) and Ni(II)-carboxylate chain in 3 (J=1.44 cm-1), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)-carboxylate chain in 4 (J=-0.77 cm-1).

  19. Synthesis, structures, luminescent and magnetic properties of four coordination polymers with the flexible 1,3-phenylenediacetate ligands

    SciTech Connect

    Gu, Jin-Zhong; Lv, Dong-Yu; Gao, Zhu-Qing; Liu, Jian-Zhao; Dou, Wei; Tang, Yu

    2011-03-15

    Four coordination polymers, [Zn(pda)(bpy)(H{sub 2}O)]{sub n}.nH{sub 2}O (1), [Cd(pda)(prz)(H{sub 2}O)]{sub n} (2), [Co{sub 3}({mu}{sub 3}-OH){sub 2}(pda){sub 2}(pyz)]{sub n}.2nH{sub 2}O (3) and [Pr{sub 2}(pda){sub 3}(H{sub 2}O){sub 2}]{sub n} (4) (H{sub 2}pda=1,3-phenylendiacetic acid, bpy=4,4'-bipyridine, prz=piperazine and pyz=pyrazine) have been hydrothermally synthesized and characterized. Complex 1 is a 1D wheel-like chain structure, which is further extended into a 3D metal-organic supramolecular framework by H-bonds and {pi}-{pi} stacking interactions. Complex 2 is a 1D ladder-like chain structure, which is also further extended into a 3D metal-organic supramolecular framework by H-bonds. Complex 3 possess a 2D sheet structure with infrequent two pairs of double-helix chains. Complex 4 features a 3D structure. Both 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of complexes 3 and 4 exhibit antiferromagnetic interactions between the nearest metal ions, with C=9.99 and 3.43 cm{sup 3} mol{sup -1} K, and {theta}=-23.9 and -46.3 K, respectively. -- Graphical abstract: Four new coordination polymers with 1,3-phenylenediacetate ligands have been hydrothermally synthesized and characterized. Complexes 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of 3 and 4 exhibit antiferromagnetic interactions between the nearest metal centers. Display Omitted Research highlights: > Coordinative property of H{sub 2}pda ligand was shown when bonded by different block metals. > Careful selection of co-ligand and metals resulted in dramatic framework evolution. > (c) The compounds constructed with Zn{sup 2+} and Cd{sup 2+} exhibit strong blue fluorescent emission. > The magneto-structural correlation of the complexes constructed with Co{sup 2+} and Pr{sup 3+} was elucidated.

  20. Silver(I) coordination polymers assembled from flexible cyclotriphosphazene ligand: structures, topologies and investigation of the counteranion effects.

    PubMed

    Davarcı, Derya; Gür, Rüştü; Beşli, Serap; Şenkuytu, Elif; Zorlu, Yunus

    2016-06-01

    The reactions of a flexible ligand hexakis(3-pyridyloxy)cyclotriphosphazene (HPCP) with a variety of silver(I) salts (AgX; X = NO3(-), PF6(-), ClO4(-), CH3PhSO3(-), BF4(-) and CF3SO3(-)) afforded six silver(I) coordination polymers, namely {[Ag2(HPCP)]·(NO3)2·H2O}n (1), {[Ag2(HPCP)(CH3CN)]·(PF6)2}n (2), {[Ag2(HPCP)(CH3CN)]·(ClO4)2}n (3), [Ag3(HPCP)(CH3PhSO3)3]n (4), [Ag2(HPCP)(CH3CN)(BF4)2]n (5) and {[Ag(HPCP)]·(CF3SO3)}n (6). All of the isolated crystalline compounds were structurally determined by X-ray crystallography. Changing the counteranions in the reactions, which were conducted under similar conditions of M/L ratio (1:1), temperature and solvent, resulted in structures with different types of topologies. In complexes (1)-(6), the ligand HPCP shows different coordination modes with Ag(I) ions giving two-dimensional layered structures and three-dimensional frameworks with different topologies. Complex (1) displays a new three-dimensional framework adopting a (3,3,6)-connected 3-nodal net with point symbol {4.6(2)}2{4(2).6(10).8(3)}. Complexes (2) and (3) are isomorphous and have a two-dimensional layered structure showing the same 3,6L60 topology with point symbol {4.2(6)}2{4(8).6(6).8}. Complex (4) is a two-dimensional structure incorporating short Ag...Ag argentophilic interactions and has a uninodal 4-connected sql/Shubnikov tetragonal plane net with {4(4).6(2)} topology. Complex (5) exhibits a novel three-dimensional framework and more suprisingly contains twofold interpenetrated honeycomb-like networks, in which the single net has a trinodal (2,3,5)-connected 3-nodal net with point symbol {6(3).8(6).12}{6(3)}{8}. Complex (6) crystallizes in a trigonal crystal system with the space group R\\bar 3 and possesses a three-dimensional polymeric structure showing a binodal (4,6)-connected fsh net with the point symbol (4(3).6(3))2.(4(6).6(6).8(3)). The effect of the counteranions on the formation of coordination polymers is discussed in this study. PMID

  1. Synthesis and crystal structure of new lanthanide coordination polymers with Pyridine-2, 6-dicarboxylic acid

    NASA Astrophysics Data System (ADS)

    Du, Rui-Zhi; Wang, Yan-Yan; Xie, Yu-Yu; Li, Hao-Tian; Liu, Tian-Fu

    2016-03-01

    Reactions between Ln(NO3)3 aq (Ln = La (1), Ce (2), Pr (3) and Nd(4)), pyridine-2, 6-dicarboxylic acid (2, 6-pdc), and sodium nitroprusside Na2[Fe(CN)5NO] lead to three-dimensional network structures: {[Ln2(2, 6-pdc)2(H2O)8][Fe(CN)5NO]·4H2O}n (Ln = La (1), Ce (2), Pr (3) and Nd(4)). The complexes 1 and 2 crystallize in the monoclinic space group Cc while complexes 3 and 4 crystallize in the monoclinic space group I2. The Ln(III) ion is nine-coordinate by four oxygen atoms of three 2, 6-pdc ligands, four oxygen of water and one nitrogen atom of 2, 6-pdc. Ln(III) ions are bridged by 2, 6-pdc ligands via bridging/chelating-bridging pentadentate coordination to form 3-D framework structures. Hydrogen bonds provide additional stabilization of the crystal structures. The magnetic properties of 2-4 have been investigated.

  2. Enantiomeric self-recognition in homo- and heterodinuclear macrocyclic lanthanide(III) complexes.

    PubMed

    Lisowski, Jerzy

    2011-06-20

    The controlled formation of lanthanide(III) dinuclear μ-hydroxo-bridged [Ln(2)L(2)(μ-OH)(2)X(2)](n+) complexes (where X = H(2)O, NO(3)(-), or Cl(-)) of the enantiopure chiral macrocycle L is reported. The (1)H and (13)C NMR resonances of these complexes have been assigned on the basis of COSY, NOESY, TOCSY, and HMQC spectra. The observed NOE connectivities confirm that the dimeric solid-state structure is retained in solution. The enantiomeric nature of the obtained chiral complexes and binding of hydroxide anions are reflected in their CD spectra. The formation of the dimeric complexes is accompanied by a complete enantiomeric self-recognition of the chiral macrocyclic units. The reaction of NaOH with a mixture of two different mononuclear lanthanide(III) complexes, [Ln(1)L](3+) and [Ln(2)L](3+), results in formation of the heterodinuclear [Ln(1)Ln(2)L(2)(μ-OH)(2)X(2)](n+) complexes as well as the corresponding homodinuclear complexes. The formation of the heterodinuclear complex is directly confirmed by the NOESY spectra of [EuLuL(2)(μ-OH)(2)(H(2)O)(2)](4+), which reveal close contacts between the macrocyclic unit containing the Eu(III) ion and the macrocyclic unit containing the Lu(III) ion. While the relative amounts of homo- and heterodinuclear complexes are statistical for the two lanthanide(III) ions of similar radii, a clear preference for the formation of heterodinuclear species is observed when the two mononuclear complexes contain lanthanide(III) ions of markedly different sizes, e.g., La(III) and Yb(III). The formation of heterodinuclear complexes is accompanied by the self-sorting of the chiral macrocyclic units based on their chirality. The reactions of NaOH with a pair of homochiral or racemic mononuclear complexes, [Ln(1)L(RRRR)](3+)/[Ln(2)L(RRRR)](3+), [Ln(1)L(SSSS)](3+)/[Ln(2)L(SSSS)](3+), or [Ln(1)L(rac)](3+)/[Ln(2)L(rac)](3+), results in mixtures of homochiral, homodinuclear and homochiral, heterodinuclear complexes. On the contrary, no

  3. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    SciTech Connect

    Gu, Jin-Zhong; Wu, Jiang; Kirillov, Alexander M.; Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai

    2014-05-01

    A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network

  4. A series of M-M' heterometallic coordination polymers: syntheses, structures and surface photoelectric properties (M=Ni/Co, M'=Cd/Zn)

    SciTech Connect

    Li, Lei; Niu, Shu-Yun; Jin, Jing; Meng, Qin; Chi, Yu-Xian; Xing, Yong-Heng; Zhang, Guang-Ning

    2011-05-15

    Four new heterometallic polymers, [NiCd(mal){sub 2}(H{sub 2}O){sub 2}]n.2nH{sub 2}O 1, [NiZn{sub 2}(Hcit){sub 2}(H{sub 2}O){sub 2}]n 2, [CoCd{sub 2}(Hcit){sub 2}(H{sub 2}O){sub 2}]n 3, [CoZn{sub 2}(Hcit){sub 2}(H{sub 2}O){sub 2}]n 4 (H{sub 2}mal=malonic acid, H{sub 4}cit=citric acid) were synthesized and characterized. The photoelectric properties of the polymers were discussed by the surface photovoltage spectroscopy (SPS). The structural analyses indicate 1 is a Ni-Cd heterometallic polymer with 3D structure bridged by the mal{sup 2-} group. 2-4 are all heterometallic polymers with 2D structures bridged by the Hcit{sup 3-} group. The results of SPS for the four polymers reveal that there are wide photovoltage response bands in the range of 300-800 nm, which indicates that they all possess photoelectric conversion properties. By the introduction of the other metals, the SPS of heterometallic polymers are broadened obviously than the SPS of monometallic complexes. Moreover, the relationships between SPS and UV-Vis absorption spectra have been discussed. -- Graphical Abstract: Four heterometallic polymers, Ni-Cd, Ni-Zn, Co-Cd, Co-Zn, were synthesized and characterized. The photoelectric properties of heterometallic polymers were discussed by SPS. The introduction of heterometallic ions will broaden the SPS of corresponded monometallic complexes. Display Omitted highlights: > Four new heterometallic coordination polymers were reported. > The surface photoelectric properties of heterometallic polymers were studied by SPS. > They all possess photoelectric conversion properties. > The SPS of heterometallic polymers are broadened than that of monometallic complexes.

  5. Structural characterization, electrochemical, photoluminescence and thermal properties of potassium ion-mediated coordination polymer.

    PubMed

    Ceyhan, Gökhan; Köse, Muhammet; Tümer, Mehmet; Dal, Hakan

    2015-05-01

    A polymeric potassium complex of p-nitrophenol was synthesized and characterized by analytical and spectroscopic techniques. Molecular structure of the complex was determined by single crystal X-ray diffraction study. X-ray structural data show that crystals contain polymeric K(+) complex of p-nitrophenol. Asymmetric unit consists of one p-nitrophenolate, one K(+) ion and one water molecule. All bond lengths and angles in the phenyl rings have normal Csp2-Csp2 values and are in the expected ranges. The p-nitrophenolate is close to planar with small distortions by some atoms. Each potassium ion in the polymeric structure is identical and eight-coordinate, bonded to four nitro, two phenolate oxygen atoms from five p-nitrophenolate ligands and two oxygen atoms from two water molecules. Electronic, electrochemical, photoluminescence and thermal properties of the complex were also investigated.

  6. Syntheses, structures and properties of four 3D microporous lanthanide coordination polymers based on 3,5-pyrazoledicarboxylate and oxalate ligands

    SciTech Connect

    Song, Juan; Wang, Ji-Jiang; Hu, Huai-Ming; Wu, Qing-Ran; Xie, Juan; Dong, Fa-Xin; Yang, Meng-Lin; Xue, Gang-Lin

    2014-04-01

    Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln{sub 2}(Hpdc){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 4}]{sub n}·2nH{sub 2}O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H{sub 3}pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H{sub 3}pdc was decomposed into (ox){sup 2−} with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2{sub 1}/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groups to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1–4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities. - Graphical abstract: Four 3D microporous lanthanide coordination polymers with reversible structural interconversion have been synthesized. They exhibit characteristic emission bands of the lanthanide ions and possess great thermal stability. - Highlights: • Four lanthanide coordination polymers have been hydrothermal synthesized. • There is an in situ reaction in 1 in which H{sub 3}pdc was decomposed into (ox){sup 2−} with the Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. • TGA and XRD studies reveal that upon hydration–dehydration, compounds 1–4 undergo a reversible structural interconversion process through a cooling-heating cycle. • Compounds 1–4 exhibit characteristic lanthanide-centered luminescence.

  7. Characteristic differences in the formation of complex coacervate core micelles from neodymium and zinc-based coordination polymers.

    PubMed

    Yan, Yun; Besseling, Nicolaas A M; de Keizer, Arie; Stuart, Martien A Cohen

    2007-05-31

    In this paper we compare the formation of complex coacervate core micelles (C3Ms) from two different tricompontent mixtures, namely neodymium, the bisligand L2EO4 and the poly(cation)-block-poly(neutral) diblock copolymer P2MVP41-b-PEO205, and zinc, L2EO4 and P2MVP41-b-PEO205 mixed systems. Three sets of titration experiments were carried out for each system: (i) titration of diblock copolymer P2MVP41-b-PEO205 with the stoichiometric mixture of metal ions and bisligands, (ii) titration of a mixture of diblock copolymer and bisligand with metal ions, and (iii) titration of a mixture of diblock copolymer and metal ions with bisligands. In all the above three cases, micelles are found to form either in a broad range of charge ratios or in a broad range of metal/bisligand ratios. Upon addition of Nd2-(L2EO4)3 coordination polymer to P2MVP41-b-PEO205 solution, and upon addition of Nd3+ to a mixture of L2EO4 and P2MVP41-b-PEO205, micelles are found to form immediately after the first addition, whereas micelles show up in the similar zinc system only after a certain threshold Zn-(L2EO4) or Zn2+ concentration. This difference can be traced to the different structures of the Nd2-(L2EO4)3 and Zn-(L2EO4) coordination compounds. At very low concentrations, Zn-(L2EO4) are ring-like oligomers, but Nd2-(L2EO4)3 are larger networks. The network structure favors the formation of coacervate micellar core with P2MVP41-b-PEO205. Moreover, excess of Nd3+ ions will break up the C3Ms, while the same amount of Zn2+ has hardly any effect on the C3Ms. The breakdown of C3Ms by Nd3+ is due to the charge inversion of the coordination complex with increasing [Nd3+]/[L2EO4] ratio, which results in repulsive interaction between the coordination complex and the diblock copolymer, whereas no such interaction can occur in the zinc system.

  8. Hydrolytic synthesis of novel lanthanide(III) complexes with pyridine-2,6-dicarboxylic acid: Characterization of the structure and the physical properties

    NASA Astrophysics Data System (ADS)

    Hojnik, Nuša; Kristl, Matjaž; Golobič, Amalija; Jagličić, Zvonko; Drofenik, Miha

    2015-01-01

    The coordination compounds of pyridine-2,6-dicarboxylic acid and two lanthanide(III) ions, Ho3+ and Dy3+, were hydrolytically synthesized in aqueous solutions at a slightly basic pH, and then characterized by thermogravimetric analysis, IR spectroscopy, magnetic measurements as well as X-ray powder and single-crystal diffraction analysis. The elemental analyses were performed to check the purity of the compounds. The formula for these compounds is identified as Na3[Ln(Pydc)3]ṡ14H2O (Ln = Ho, 1; Ln = Dy, 2) in agreement with the X-ray structural analysis and all the other experimental data. The absence of the 1709 cm-1 band corresponding to ν(C dbnd O) in the IR spectra of the compounds evidences the deprotonating of the carboxyl group. The very strong inductive effect of the metal ion that is readily coordinated by the carboxylate group of the zwitterionic ligand is responsible for the formation of the product. The single-crystal X-ray structural analysis revealed that compounds 1 and 2 are isostructural. Their structure can be described as interchanging layers of complex anions [Ln(Pydc)3]3 (Ln = Ho and Dy for 1 and 2, respectively) and layers of hydrated sodium cations. In complex anions the holmium and dysprosium atoms are coordinated by three crystallographically independent pyridinedicarboxylate ligands in tridentate-chelate mode, via one O atom of both carboxylate groups and the ring N atom. The coordination number is nine and the coordination polyhedron is a tricapped trigonal prism with O atoms at the corners.

  9. High resolution scanning tunneling microscopy of a 1D coordination polymer with imidazole-based N,N,O ligands on HOPG.

    PubMed

    Fischer, Nina V; Mitra, Utpal; Warnick, Karl-Georg; Dremov, Viacheslav; Stocker, Michael; Wölfle, Thorsten; Hieringer, Wolfgang; Heinemann, Frank W; Burzlaff, Nicolai; Görling, Andreas; Müller, Paul

    2014-09-01

    Novel κ(3) -N,N,O ligands tend to form 1D coordination polymer strands. Deposition of 1D structures on highly oriented pyrolytic graphite (HOPG) was achieved from diluted solutions and polymer strands have been studied on HOPG by AFM/STM. Single strands were mapped by STM and their electronic properties were subsequently characterized by current imaging tunneling spectroscopy (CITS). Periodic density functional calculations simulating a polymer strand deposited on a HOPG surface are in agreement with the zig-zag structure indicated by experimental findings. Both the observed periodicity and the Zn-Zn distances can be reproduced in the simulations. Van der Waals interactions were found to play a major role for the geometry of the isolated polymer strand, for the adsorption geometry on HOPG, as well as for the adsorption energy.

  10. Three new homochiral coordination polymers involving two three-dimensional structural architectures: Syntheses, structures and magnetic properties

    SciTech Connect

    Chao, Tzu-Ling; Yang, Chen-I.

    2014-03-15

    The preparations and properties of three new homochiral three-dimensional (3D) coordination polymers, [M(D-cam)(pyz)(H{sub 2}O){sub 2}]{sub n} (M=Co (1) and Ni (2); D-H{sub 2}cam=(+) D-camphoric acid; pyz=pyrazine) and [Mn{sub 2}(D-cam){sub 2}(H{sub 2}O){sub 2}] (3), under solvothermal conditions is described. Single-crystal X-ray diffraction analyses revealed that all of compounds are homochiral 3D structure. 1 and 2 are isostructural and crystallize in the trigonal space group P3{sub 2}21, while 3 crystallizes in monoclinic space group P2{sub 1}. The structure of 1 and 2 consists of metal-D-cam helical chains which are pillared with pyrazine ligands into a 3D framework structure and 3 features a 3D homochiral framework involving one-dimensional manganese-carboxylate chains that are aligned parallel to the b axis. Magnetic susceptibility data of all compounds were collected. The findings indicate that μ{sub 2}-pyrazine dominate weak antiferromagnetic coupling within 1 and 2, while 3 exhibits antiferromagnetic behavior through the carboxylate groups of D-cam ligand. -- Graphical abstract: The preparations and properties of three new homochiral three-dimensional (3D) coordination polymers, [M(D-cam)(pyz)(H{sub 2}O){sub 2}]{sub n} (M=Co (1) and Ni (2); D-H{sub 2}cam=(+) D-camphoric acid; pyz=pyrazine) and [Mn{sub 2}(D-cam){sub 2}(H{sub 2}O){sub 2}] (3), under solvothermal conditions is described. Single-crystal X-ray diffraction analyses revealed that all of compounds are homochiral 3D structure. 1 and 2 are isostructural and crystallize in the trigonal space group P3{sub 2}21, while 3 crystallizes in monoclinic space group P2{sub 1}. The structure of 1 and 2 consists of metal-D-cam helical chains which are pillared with pyrazine ligands into a 3D framework structure and 3 features a 3D homochiral framework involving one-dimensional manganese-carboxylate chains that are aligned parallel to the b axis. Magnetic susceptibility data of all compounds were collected. The

  11. In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids.

    PubMed

    Ellis, Ross J; Demars, Thomas; Liu, Guokui; Niklas, Jens; Poluektov, Oleg G; Shkrob, Ilya A

    2015-09-01

    Coordination polymers (CPs) of metal ions are central to a large variety of applications, such as catalysis and separations. These polymers frequently occur as amorphous solids that segregate from solution. The structural aspects of this segregation remain elusive due to the dearth of the spectroscopic techniques and computational approaches suitable for probing such systems. Therefore, there is a lacking of understanding of how the molecular building blocks give rise to the mesoscale architectures that characterize CP materials. In this study we revisit a CP phase formed in the extraction of trivalent lanthanide ions by diesters of the phosphoric acid, such as the bis(2-ethylhexyl)phosphoric acid (HDEHP). This is a well-known system with practical importance in strategic metals refining and nuclear fuel reprocessing. A CP phase, referred to as a "third phase", has been known to form in these systems for half a century, yet the structure of the amorphous solid is still a point of contention, illustrating the difficulties faced in characterizing such materials. In this study, we follow a deductive approach to solving the molecular structure of amorphous CP phases, using semiempirical calculations to set up an array of physically plausible models and then deploying a suite of experimental techniques, including optical, magnetic resonance, and X-ray spectroscopies, to consecutively eliminate all but one model. We demonstrate that the "third phase" consists of hexagonally packed linear chains in which the lanthanide ions are connected by three O-P-O bridges, with the modifying groups protruding outward, as in a bottlebrush. The tendency to yield linear polynuclear oligomers that is apparent in this system may also be present in other systems yielding the "third phase", demonstrating how molecular geometry directs polymeric assembly in hybrid materials. We show that the packing of bridging molecules is central to directing the structure of CP phases and that by

  12. The new one-dimensional coordination polymer catena-poly[[diaquasodium(I)]-μ-oxalato-[diaquairon(III)]-μ-oxalato].

    PubMed

    Benhacine, Mohamed Al Amine; Hamadène, Malika; Bouacida, Sofiane; Merazig, Hocine

    2016-03-01

    The oxalate dianion is one of the most studied ligands and is capable of bridging two or more metal centres and creating inorganic polymers based on the assembly of metal polyhedra with a wide variety of one-, two- or three-dimensional extended structures. Yellow single crystals of a new mixed-metal oxalate, namely catena-poly[[diaquasodium(I)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')-[diaquairon(III)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')], [NaFe(C2O4)2(H2O)4]n, have been synthesized and the crystal structure elucidated by X-ray diffraction analysis. The compound crystallizes in the noncentrosymmetric space group I41 (Z = 4). The asymmetric unit contains one Na(I) and one Fe(III) atom lying on a fourfold symmetry axis, one μ2-bridging oxalate ligand and two aqua ligands. Each metal atom is surrounded by two chelating oxalate ligands and two equivalent water molecules. The structure consists of infinite one-dimensional chains of alternating FeO4(H2OW1)2 and NaO4(H2OW2)2 octahedra, bridged by oxalate ligands, parallel to the [100] and [010] directions, respectively. Because of the cis configuration and the μ2-coordination mode of the oxalate ligands, the chains run in a zigzag manner. This arrangement facilitates the formation of hydrogen bonds between neighbouring chains involving the H2O and oxalate ligands, leading to a two-dimensional framework. The structure of this new one-dimensional coordination polymer is shown to be unique among the A(I)M(III)(C2O4)2(H2O)n series. In addition, the absorption bands in the IR and UV-Visible regions and their assignments are in good agreement with the local symmetry of the oxalate ligand and the irregular environment of iron(III). The final product of the thermal decomposition of this precursor is the well-known ternary oxide NaFeO2. PMID:26942436

  13. Uranyl sensitization of samarium (III) luminescence in a two-dimensional coordination polymer

    SciTech Connect

    Knope, Karah E.; de Lill, Daniel T.; Rowland, Clare E.; Cantos, Paula M.; de Bettencourt-Dias, Ana; Cahill, Christopher L.

    2012-01-02

    Heterometallic carboxyphosphonates UO₂2+/Ln3+ have been prepared from the hydrothermal reaction of uranyl nitrate, lanthanide nitrate (Ln = Sm, Tb, Er, Yb), and phosphonoacetic acid (H₃PPA). Compound 1, (UO₂)₂(PPA)(HPPA)₂Sm(H₂O)·2H₂O (1) adopts a two-dimensional structure in which the UO₂2+ metal ions bind exclusively to the phosphonate moiety, whereas the Ln3+ ions are coordinated by both phosphonate and carboxylate functionalities. Luminescence studies of 1 show very bright visible and near-IR samarium(III)-centered emission upon direct excitation of the uranyl moiety. The Sm3+ emissive state exhibits a double-exponential decay with lifetimes of 67.2 ± 6.5 and 9.0 ± 1.3 μs as measured at 594 nm, after excitation at both 365 and 420 nm. No emission is observed in the region typical of the uranyl cation, indicating that all energy is either transferred to the Sm3+ center or lost to nonradiative processes. Herein we report the synthesis, crystal structure, and luminescent behavior of 1, as well as those of the isostructural terbium, erbium, and ytterbium analogues.

  14. Three coordination polymers based on different carboxylates, metals and a tri(4-imidazolylphenyl)amine ligand

    NASA Astrophysics Data System (ADS)

    Wu, Hua; Shi, Chenjie; Zhao, Yanqing; Jiang, Yutong; Tao, Yuehong

    2015-04-01

    In this paper, three new coordination complexes based on a flexible tri(4-imidazolylphenyl)amine (Tipa) ligand, namely [Co(Tipa)(L1)2]·H2O (1), [Zn2(Tipa)(L1)4(H2O)]·2H2O (2) and [Mn(Tipa)(L2)]·2H2O (3), where HL1 = benzoic acid H2L2 = 5-OH-1,3-benzenedicarboxylic acid and Tipa = tri(4-imidazolylphenyl)amine, have been synthesized under the hydrothermal condition and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectra. Compound 1 exhibits a 1D ladder chain with the benzoic anions hanging on the two sides of the chain. For compound 2, it shows a fascinating 1D zigzag chain. Compound 3 displays (3,5)-connected (42·6)(42·67·8) topology, where the identical 2D networks entangle in highly rare parallel fashions to give a fascinating 2D → 3D framework with polycatenation and polyrotaxane characters. Moreover, the photoluminescent properties for the compounds 2 and 3 were also investigated.

  15. Electronic, optical, and computational studies of a redox-active napthalenediimide-based coordination polymer.

    PubMed

    Leong, Chanel F; Chan, Bun; Faust, Thomas B; Turner, Peter; D'Alessandro, Deanna M

    2013-12-16

    The new one-dimensional coordination framework (Zn(DMF)NO3)2(NDC)(DPMNI), where NDC = 2,6-naphthalenedicarboxylate and DPMNI = N,N'-bis(4-pyridylmethyl)-1,4,5,8-naphthalenetetracarboxydiimide, which has been crystallographically characterized, exhibits two redox-accessible states due to the successive reduction of the naphthalenediimide (NDI) ligand core. Solid-state electrochemical and vis-near-IR spectroelectrochemical measurements coupled with density functional theory (DFT) calculations enabled the origins of the optical transitions in the spectra of the monoradical anion and dianion states of the material to be assigned. Electron paramagnetic resonance (EPR) spectroscopy revealed that the paramagnetic radical anion state of the DPMNI core could be accessed upon broad-spectrum white light irradiation of the material, revealing a long-lived excited state, possibly stabilized by charge delocalization which arises from extensive π-π* stacking interactions between alternating NDC and NDI aromatic cores which are separated by a distance of 3.580(2) Å. PMID:24283401

  16. Two new pyridine-2,3-dicarboxylate coordination polymers prepared from zerovalent metal precursor: Syntheses, luminescent and magnetic properties

    SciTech Connect

    Semerci, Fatih; Yeşilel, Okan Zafer; Soylu, Mustafa Serkan; Yerli, Yusuf; Dal, Hakan

    2014-02-15

    Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. In the sandwiched 3D anionic framework of 1, pydc ligands exhibit hexadentate coordination; tridentate coordination bond with Cu(II) and tridentate ionic interaction with K{sup +} ions. (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows a rare topology consists of three dimensional (3,4,5)-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The distorted square pyramidal geometry of 2 is completed with an nitrogen atom from 4-mim and aqua ligand to form a 1D polynuclear structure. The hydrogen bonds link the 1D chains into 3D architecture. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. - Graphical abstract: Two new K{sup +}/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} (1) and ([Zn(µ-pydc)(H{sub 2}O)(4-mim)]·H{sub 2}O){sub n} (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. The water soluble (K{sub 2}[Cu(μ-pydc){sub 2}]·3H{sub 2}O){sub n} shows three dimensional a rare 3,4,5-connected network with the point symbol of (4{sup 2}.6){sub 2}(4{sup 2}.8{sup 4})(4{sup 3}.6.8{sup 6}){sub 2}. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature. Display Omitted - Highlights: • Water

  17. Cadmium and zinc chain and cluster-based layered coordination polymers prepared from flexible-arm aromatic ortho-dicarboxylic acids and 4-pyridylnicotinamide

    NASA Astrophysics Data System (ADS)

    Kraft, Peter E.; Uebler, Jacob W.; LaDuca, Robert L.

    2013-04-01

    Hydrothermal reaction of a d10-metal nitrate salt, a flexible-arm aromatic ortho-dicarboxylic acid, and 4-pyridylnicotinamide (4-pna) afforded four new crystalline coordination polymers, which were characterized by single-crystal X-ray diffraction. [Cd(Hhmph)(nic)(H2O)2]n (1, hmph = homophthalate, nic = nicotinate) is a 1-D coordination polymer chain compound whose nic ligands were generated in situ via 4-pna hydrolysis. Addition of base and a shorter reaction duration afforded [Cd(hmph)(4-pna)]n (2), which has dinuclear [Cd2(hmph)2] dimers linked into a 1-D ladder polymer via 4-pna ligands. A similar chain structure, albeit with a different hmph binding mode, is seen in [Zn(hmph)(4-pna)]n (3). {[Zn2(phda)2(4-pna)2(H2O)]ṡH2O}n (4, phda = 1,2-phenylenediacetate) has both anti-syn bridged [Zn2(OCO)2] ring dimers and [Zn2(OCO)4] paddlewheel dimers, linked into a layered coordination polymer by dipodal 4-pna ligands. Luminescent properties of these new materials are also presented.

  18. Coordination bonding construction, characterization and photoluminescence of ternary lanthanide (Eu(3+), Tb(3+)) hybrids with phenylphenacyl-sulfoxide modified bridge and polymer units.

    PubMed

    Guo, Lei; Yan, Bing; Liu, Jin-Liang; Sheng, Kai; Wang, Xiao-Long

    2011-01-21

    A novel polysilsesquioxane bridge (PPSSi) is synthesized with methylene group modification of phenylphenacyl sulfoxide by isocyanate group from 3-(triethoxysilyl)propyl isocyanate (TEPIC). Then ternary lanthanide (Eu, Tb) hybrids of polysilsesquioxane bridge (PPSSi) and four kinds of polymer chain (polyacrylamide (PAM), polyvinylpyrrolidone (PVP), polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA) were assembled wth coordination bonding. To explore the influence of the different polymeric chains on the properties of lanthanide hybrids, the microstructure and photoluminescent properties of these lanthanide coordination polymer hybrids (PPSSi-Ln-PAM (PVP, PMMA, PEMA)) are compared in detail. Four organic polymer chains with different structures not only can coordinate to the lanthanide ions by their own carbonyl groups, but also can form a polymeric matrix together with the inorganic Si-O network. The results show that all the obtained hybrids could show efficient intramolecular energy transfer and lead to excellent characteristic emission of lanthanide ions. Moreover, the different structures of the polymers induce different microstructures and different photoluminescent behavior (lifetime and quantum efficiency) for these hybrid systems. The PPSSi-Ln-PMMA hybrid leads to the longest lifetime and highest quantum efficiency.

  19. Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

    PubMed Central

    Yan, Xuzhou; Li, Shijun; Pollock, James Bryant; Cook, Timothy R.; Chen, Jianzhuang; Zhang, Yanyan; Ji, Xiaofan; Yu, Yihua; Huang, Feihe; Stang, Peter J.

    2013-01-01

    A powerful strategy to obtain complex supramolecular materials is the bottom-up construction of noncovalently bound materials by hierarchical self-assembly. This assembly process involves stepwise, uniform increases to the architectural complexity of a substrate, starting from discrete precursors and growing in dimensionality through controlled reactivity to a final product. Herein, two orthogonal processes are exploited: coordination-driven self-assembly and hydrogen bonding. The former relies on the predictable formation of metal–ligand bonds wherein the directionalities of the rigid precursors used determines the structural outcome. The latter uses 2-ureido-4-pyrimidinone interfaces that are structurally robust by virtue of the quadruple hydrogen bonding that can occur between subunits. By combining these two processes into a single system, it is possible to generate hierarchical materials that preserve the attractive tunability associated with discrete supramolecular coordination complexes. For instance, the synthesis of a one-dimensional chain comprising linked metalla-rhomboids is readily adapted to a 2D cross-linked hexagonal network by simply selecting a different metal acceptor precursor as an assembly component. The specific interactions between subunits, in this case platinum(II)-pyridyl bonds and the quadruple H-bonding of ureidopyrimidinone, are unchanged, establishing a unique strategy to obtain supramolecular polymers with marked topological differences with minimal synthetic redesign. In addition, the structural rigidity imposed by the inclusion of the platinum metallacycles serves to minimize the formation of cyclic oligomers, increasing the efficacy of formation and improving the properties of the resultant materials. Furthermore, this study taps the potential of organoplatinum(II) metallacycles in materials science. PMID:24019475

  20. Extending framework based on the linear coordination polymers: Alternative chains containing lanthanum ion and acrylic acid ligand

    NASA Astrophysics Data System (ADS)

    Li, Hui; Guo, Ming; Tian, Hong; He, Fei-Yue; Lee, Gene-Hsiang; Peng, Shie-Ming

    2006-11-01

    One-dimensional alternative chains of two lanthanum complexes: [La( L1) 3(CH 3OH)(H 2O) 2]·5H 2O ( L1=anion of α-cyano-4-hydroxycinnamic acid ) 1 and [La( L2) 3(H 2O) 2]·3H 2O ( L2=anion of trans-3-(4-methyl-benzoyl)-acrylic acid) 2 were synthesized and structurally characterized by single-crystal X-ray diffraction, element analysis, IR and thermogravimetric analysis. The crystal structure data are as follows for 1: C 31H 36LaN 3O 17, triclinic, P-1, a=9.8279(4) Å, b=11.8278(5) Å, c=17.8730(7) Å, α=72.7960(10)°, β=83.3820(10)°, γ=67.1650(10)º, Z=2, R1=0.0377, wR2=0.0746; for 2: C 33H 37LaO 14, triclinic, P-1, a=8.7174(5) Å, b=9.9377(5) Å, c=21.153(2) Å, α=81.145(2)°, β=87.591(2)°, γ=67.345(5)°, Z=2, R1=0.0869, wR2=0.220. 1 is a rare example of the alternative chain constructed by syn-syn and anti-syn coordination mode of carboxylato ligand arranged along the chain alternatively. La(III) ions in 2 are linked by two η3-O bridges and four bridges (two η2-O and two η3-O) alternatively. Both of the linear coordination polymers grow into two- and three-dimensional networks by packing through extending hydrogen-bond network directed by ligands.

  1. Influence of the steric effect of flexible isomeric phenylenediacetic acids on the resultant lead(II) coordination polymers

    NASA Astrophysics Data System (ADS)

    Wu, Yunlong; Zhao, Yanqing; Yang, Guo-Ping; Guo, Yanjun; Wang, Yao-Yu; Shi, Qi-Zhen

    2015-03-01

    To study the steric effect of the flexible dicarboxylate ligands on the resultant formations of coordination polymers (CPs), four new PbII CPs [Pb(1,2-pda)(H2O)]n (1), [Pb(1,3-pda)]n·nH2O (2), [Pb2(1,4-pda)2(H2O)]n·2nH2O (3a and 3b) have been produced by the isomeric phenylenediacetic acids (H2pda). The X-ray crystallography study reveals that CP 1 is a two-dimensional (2D) 4-connected sql (44.62) network via the weak Pb···O interactions built on 1D chain-like structure. CP 2 crystallizes in orthorhombic system with chiral space group P212121, showing a 4-connected sra (42.63.8) framework where a left-handed helical motif is formed by PbII ions and trans-1,3-pda ligands. More interestingly, CPs 3a and 3b are two true 3D polymorphs and have the different morphology. Topologically, the framework of 3a exhibits a 4-connected lon 66 motif, while that of 3b is a (4,6)-connected fsh (43.63)2(46.66.83) net. It is found that the three isomeric pda anions display the various coordination fashions in four CPs. The different structural arrangements show that the steric effect of the isomeric H2pda tectons has a positive role in directing the final products of PbII CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature.

  2. Three polymorphic Cd(II) coordination polymers obtained from the solution and mechanochemical reactions of 3-cyanopentane-2,4-dione with Cd(II) acetate.

    PubMed

    Yoshida, Jun; Nishikiori, Shin-ichi; Kuroda, Reiko; Yuge, Hidetaka

    2013-03-01

    We previously reported that monomeric and polymeric metal complexes are obtained from solution and mechanochemical reactions of 3-cyano-pentane-2,4-dione (CNacacH) with 3d metal acetates (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)). A common feature found in all complexes was that their structural base is trans-[M(CNacac)(2)]. Here, we report that the reactions of CNacacH with Cd(II) acetate in the solution and solid states afford different coordination polymers composed of trans-[Cd(CNacac)(2)] and cis-[Cd(CNacac)(2)] units, respectively. From a methanol solution containing CNacacH (L) and Cd(OAc)(2)⋅2 H(2)O (M), a coordination polymer (Cd-1) in which trans-[Cd(CNacac)(2)] units are three-dimensionally linked was obtained. In contrast, two different coordination polymers, Cd-2 and Cd-3, were obtained from mechanochemical reactions of CNacacH with Cd(OAc)(2)⋅2 H(2)O at M/L ratios of 1:1 and 1:2, respectively. In Cd-2, cis-[Cd(CNacac)(2)] units are two-dimensionally linked, whereas the units are linked three-dimensionally in Cd-3. Furthermore, Cd-1 and Cd-2 converted to Cd-3 by applying an annealing treatment and grinding with a small amount of liquid, respectively, in spite of the polymeric structures. These phenomena, 1) different structures are formed from solution and mechanochemical reactions, 2) two polymorphs are formed depending on the M/L ratio, and 3) structural transformation of resulting polymeric structures, indicate the usability of mechanochemical method in the syntheses of coordination polymers as well as the peculiar structural flexibility of cadmium-CNacac polymers.

  3. Synthesis and characterization of different zinc(II) oxide nano-structures from two new zinc(II)-Quinoxaline coordination polymers

    NASA Astrophysics Data System (ADS)

    Molaei, Fatemeh; Bigdeli, Fahime; Morsali, Ali; Joo, Sang Woo; Bruno, Giuseppe; Rudbari, Hadi Amiri

    2015-09-01

    Two new zinc(II) coordination polymers, [Zn(Quinoxaline)(NO3)2(H2O)2]nṡQuinoxaline·H2O (1) and [Zn(Quinoxaline)2(Br)2]n (2), Quinoxaline = Benzopyrazine, have been synthesized and characterized by IR spectroscopy. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and are one-dimensional coordination polymers with coordination environment of octahedral and tetrahedral respectively. Nanostructures of zinc(II) oxide were obtained by thermolyses of compound 1 in oleic acid, calcination of compound 1 at 500 °C under air atmosphere and sol-gel processes. Also, nanopowders of zinc(II) oxide were obtained by calcination of compound 2 at 450 and 550 °C. The nanomaterials were characterized by scanning electron microscopy and X-ray powder diffraction (XRD). The thermal stability of compounds 1 and 2 both their bulk were studied by thermo-gravimetric (TGA) and differential thermal analyses (DTA). This study demonstrates the coordination polymers may be suitable precursors for the preparation of nanoscale materials.

  4. pH- and mol-ratio dependent formation of zinc(II) coordination polymers with iminodiacetic acid: Synthesis, spectroscopic, crystal structure and thermal studies

    SciTech Connect

    Ni Lubin; Zhang Ronghua; Liu Qiongxin; Xia Wensheng; Wang Hongxin; Zhou Zhaohui

    2009-10-15

    Three novel zinc coordination polymers (NH{sub 4}){sub n}[Zn(Hida)Cl{sub 2}]{sub n} (1), [Zn(ida)(H{sub 2}O){sub 2}]{sub n} (2), [Zn(Hida){sub 2}]{sub n}.4nH{sub 2}O (3) (H{sub 2}ida=iminodiacetic acid) and a monomeric complex [Zn(ida)(phen)(H{sub 2}O)].2H{sub 2}O (4) (phen=1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction methods. 1 and 2 form one-dimensional (1-D) chain structures, whereas 3 exhibits a three-dimensional (3-D) diamondoid framework with an open channel. The mononuclear complex 4 is extended into a 3-D supramolecular architecture through hydrogen bonds and pi-pi stacking. Interestingly, cyclic nonplanar tetrameric water clusters are observed that encapsulated in the 3-D lattice of 4. Based on {sup 1}H and {sup 13}C NMR observations, there is obvious coordination of complex 2 in solution, while 1 and 3 decompose into free iminodiacetate ligand. Monomer [Zn(ida)(H{sub 2}O){sub 3}] (5) is considered as a possible discrete species from 2. These coordination polymers can serve as good molecular precursors for zinc oxide. - Text3: Reaction of zinc salt with iminodiacetic acid afforded three new coordination polymers 1-3 and a monomer 4, which is dependent on pH value and molar ratio of the reactants.

  5. A novel polythreading Ag(I) coordination polymer with blue photoluminescence

    SciTech Connect

    Duan, Xian-Ying; Yao, Jing; Lu, Chang-Sheng; Meng, Qing-Jin

    2013-04-15

    One new compound, [Ag(p-bix)]{sub 3}[Ag(Hbtc){sub 2}]·2H{sub 2}O (H{sub 3}btc=1,2,4-benzenetricarboxylate, p-bix=1,4-bis(imidazol-1-ylmethyl)-benzene), has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, PXRD, luminescent analysis, and single-crystal X-ray diffraction. X-ray structural analysis revealed that 0-D unit [Ag(Hbtc){sub 2}]{sup 3−} and two kinds of 1-D linear chain [Ag(p-bix)]{sub ∞}{sup +}, can be found within the crystal structure. The combination of 0-D [Ag(Hbtc){sub 2}]{sup 3−} unit and 1-D undulated chain [Ag1(p{sub 1}-bix)]{sub ∞}{sup +} through weak Ag–O bond gave rise to 2-D anionic supramolecular doublelayer. Then the grids of the 2-D layer are threaded by 1-D linear cationic chain [Ag2(p{sub 2}-bix)]{sub ∞}{sup +} to generate entangled 3-D architecture with unusual poly(pseudo-rotaxane)-type arrangements. Luminescent properties of the title complex were also studied in this paper. - Graphical abstract: Novel 3D polythreading supramolecular architecture was constructed, in which 1D linear cationic chains [Ag(p{sub 2}-bix)]{sub ∞}{sup +} threaded into the grid of weak Ag–O bonded anionic 2D sheet. Highlights: ► Novel 1D{sup +}+2D{sup −}→3D polythreading coordination complex was reported. ► Diverse conformations of p-bix result in different 1D [Ag(p-bix)]{sub ∞}{sup +} chains. ► The title complex displayed blue photoluminescence at room temperature.

  6. Robust Cross-Linked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization.

    PubMed

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y-X

    2016-08-01

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust cross-linked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site-controlled propagation mechanism. Postfunctionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible cross-linked thin-film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Cross-linking of such complexes affords robust cross-linked stereocomplexes that are solvent-resistant and also exhibit considerably enhanced thermal and mechanical properties compared with the un-cross-linked stereocomplexes. PMID:27388024

  7. Polymers.

    ERIC Educational Resources Information Center

    Tucker, David C.

    1986-01-01

    Presents an open-ended experiment which has students exploring polymer chemistry and reverse osmosis. This activity involves construction of a polymer membrane, use of it in a simple osmosis experiment, and application of its principles in solving a science-technology-society problem. (ML)

  8. Effect of pH on complex coacervate core micelles from Fe(III)-based coordination polymer.

    PubMed

    Wang, Junyou; de Keizer, Arie; van Leeuwen, Herman P; Yan, Yun; Vergeldt, Frank; van As, Henk; Bomans, Paul H H; Sommerdijk, Nico A J M; Cohen Stuart, Martien A; van der Gucht, Jasper

    2011-12-20

    The effect of pH on iron-containing complex coacervate core micelles [Fe(III)-C3Ms] is investigated in this paper. The Fe(III)-C3Ms are formed by mixing cationic poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) [P2MVP(41)-b-PEO(205)] and anionic iron coordination polymers [Fe(III)-L(2)EO(4)] at stoichiometric charge ratio. Light scattering and Cryo-TEM have been performed to study the variations of hydrodynamic radius and core structure with changing pH. The hydrodynamic radius of Fe(III)-C3Ms is determined mainly by the corona and does not change very much in a broad pH range. However, Cryo-TEM pictures and magnetic relaxation measurements indicate that the structure of the micellar cores changes upon changing the pH, with a more crystalline, elongated shape and lower relaxivity at high pH. We attribute this to the formation of mixed iron complexes in the core, involving both the bis-ligand and hydroxide ions. These complexes are stabilized toward precipitation by the diblock copolymer.

  9. Self-assembled nanoscale coordination polymers carrying siRNAs and cisplatin for effective treatment of resistant ovarian cancer.

    PubMed

    He, Chunbai; Liu, Demin; Lin, Wenbin

    2015-01-01

    Resistance to the chemotherapeutic agent cisplatin is a major limitation for the successful treatment of many cancers. Development of novel strategies to overcome intrinsic and acquired resistance to chemotherapy is of critical importance to effective treatment of ovarian cancer and other types of cancers. We have sought to re-sensitize resistant ovarian cancer cells to chemotherapy by co-delivering chemotherapeutics and pooled siRNAs targeting multi-drug resistance (MDR) genes using self-assembled nanoscale coordination polymers (NCPs). In this work, NCP-1 particles with trigger release properties were first constructed by linking cisplatin prodrug-based bisphosphonate bridging ligands with Zn(2+) metal-connecting points and then coated with a cationic lipid layer, followed by the adsorption of pooled siRNAs targeting three MDR genes including survivin, Bcl-2, and P-glycoprotein via electrostatic interactions. The resulting NCP-1/siRNA particles promoted cellular uptake of cisplatin and siRNA and enabled efficient endosomal escape in cisplatin-resistant ovarian cancer cells. By down-regulating the expression of MDR genes, NCP-1/siRNAs enhanced the chemotherapeutic efficacy as indicated by cell viability assay, DNA ladder, and flow cytometry. Local administration of NCP-1/siRNAs effectively reduced tumor sizes of cisplatin-resistant SKOV-3 subcutaneous xenografts. This work shows that the NCP-1/siRNA platform holds great promise in enhancing chemotherapeutic efficacy for the effective treatment of drug-resistant cancers.

  10. Azine bridged silver coordination polymers: Powder X-ray diffraction route to crystal structure determination of silver benzotriazole

    SciTech Connect

    Rajeswaran, Manju . E-mail: manju.rajeswaran@kodak.com; Blanton, Thomas N.; Giesen, David J.; Whitcomb, David R.; Zumbulyadis, Nicholas; Antalek, Brian J.; Neumann, Marcus M.; Misture, Scott T.

    2006-04-15

    In continuation of our interest in solid-state structures of silver complexes of photographic importance, the structure for silver benzotriazole (AgBZT), has now been obtained. The preferred method for solving crystal structures is via single-crystal X-ray diffraction (XRD). However, for some materials, growing single crystals of appropriate size and quality is often difficult or even impossible. AgBZT is an example of such a silver complex with poor solubility. The usual routes to preparing single crystals using recrystallization from a cooperating solvent resulted in polycrystalline powder samples. We propose a crystal structure for AgBZT, solved from synchrotron X-ray powder diffraction data, using a direct-space Monte Carlo simulated annealing approach. AgBZT crystals are monoclinic (P2{sub 1} /c), with unit cell dimensions, a=14.8052(3) A, b=3.7498(4) A, c=12.3495(12) A, and {beta}=114.200(6){sup o}. The AgBZT complex is constructed from all three of the Benzotriazole (BZT) nitrogens bonding to a separate silver atom. As a consequence of this bonding mode, the structure is a highly cross-linked, coordination polymer.

  11. Mono/bimetallic water-stable lanthanide coordination polymers as luminescent probes for detecting cations, anions and organic solvent molecules.

    PubMed

    Wang, Huarui; Qin, Jianhua; Huang, Chao; Han, Yanbing; Xu, Wenjuan; Hou, Hongwei

    2016-08-01

    Eleven water-stable isostructural mono/bimetallic lanthanide coordination polymers (Ln-CPs) {[EuxTb1-x (HL)(H2O)3]·H2O}n (x = 1.0 (1), 0.9 (3), 0.8 (4), 0.7 (5), 0.6 (6), 0.4 (7), 0.3 (8), 0.2 (9), 0.1 (10), 0.05 (11), 0 (2), H4L = 5,5'-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid) with uncoordinated Lewis basic triazole sites within the pores were prepared. The Ln-CPs represented by 1 showed a rapid and drastic emission quenching induced by external Fe(3+) and Cr(3+) cations and CrO4(2-) and CO3(2-) anions in aqueous solution. In addition, because of the comparable emission intensities of Eu(3+) and Tb(3+) ions, bimetallic CP 8 can be used as a ratiometric luminescent sensor for organic solvent molecules. Moreover, the luminescent color of the 8 sensor in pyridine and in other guest solvents undergoes obvious changes that can be clearly distinguished by the naked eye. PMID:27443408

  12. Sonochemical synthesis of a new nano-sized cerium(III) coordination polymer and its conversion to nanoceria.

    PubMed

    Derakhshandeh, Parviz Gohari; Soleimannejad, Janet; Janczak, Jan

    2015-09-01

    Nanoparticles of a new two-dimensional cerium(III) coordination polymer compound, [Ce(pzdc)(pzdcH)(H2O)3]n (1), (H2pzdc=2,3-pyrazinedicarboxylic acid), have been synthesized by a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses. Compound 1 was structurally characterized by single crystal X-ray diffraction and was shown that it consists of 2D sheets that construct a three-dimensional supramolecular architecture via non-covalent interactions i.e. hydrogen bonding. The thermal stability of compound 1 both for its crystals and nanostructures has been studied by the thermal gravimetric (TG) method and compared with each other. The role of ultrasound irradiation power and the concentration of initial reactants on the size and morphology of the nano-structured compound 1, has been investigated. Calcination of compound 1 at 800°C under air atmosphere yields ceria nanoparticles. Furthermore, the fluorescent properties of compound 1 at room temperature were studied.

  13. Core-shell nanoscale coordination polymers combine chemotherapy and photodynamic therapy to potentiate checkpoint blockade cancer immunotherapy

    NASA Astrophysics Data System (ADS)

    He, Chunbai; Duan, Xiaopin; Guo, Nining; Chan, Christina; Poon, Christopher; Weichselbaum, Ralph R.; Lin, Wenbin

    2016-08-01

    Advanced colorectal cancer is one of the deadliest cancers, with a 5-year survival rate of only 12% for patients with the metastatic disease. Checkpoint inhibitors, such as the antibodies inhibiting the PD-1/PD-L1 axis, are among the most promising immunotherapies for patients with advanced colon cancer, but their durable response rate remains low. We herein report the use of immunogenic nanoparticles to augment the antitumour efficacy of PD-L1 antibody-mediated cancer immunotherapy. Nanoscale coordination polymer (NCP) core-shell nanoparticles carry oxaliplatin in the core and the photosensitizer pyropheophorbide-lipid conjugate (pyrolipid) in the shell (NCP@pyrolipid) for effective chemotherapy and photodynamic therapy (PDT). Synergy between oxaliplatin and pyrolipid-induced PDT kills tumour cells and provokes an immune response, resulting in calreticulin exposure on the cell surface, antitumour vaccination and an abscopal effect. When combined with anti-PD-L1 therapy, NCP@pyrolipid mediates regression of both light-irradiated primary tumours and non-irradiated distant tumours by inducing a strong tumour-specific immune response.

  14. Silver coordination polymers for prevention of implant infection: thiol interaction, impact on respiratory chain enzymes, and hydroxyl radical induction.

    PubMed

    Gordon, Oliver; Vig Slenters, Tünde; Brunetto, Priscilla S; Villaruz, Amer E; Sturdevant, Daniel E; Otto, Michael; Landmann, Regine; Fromm, Katharina M

    2010-10-01

    Prosthetic joint replacements are used increasingly to alleviate pain and improve mobility of the progressively older and more obese population. Implant infection occurs in about 5% of patients and entails significant morbidity and high social costs. It is most often caused by staphylococci, which are introduced perioperatively. They are a source of prolonged seeding and difficult to treat due to antibiotic resistance; therefore, infection prevention by prosthesis coating with nonantibiotic-type anti-infective substances is indicated. A renewed interest in topically used silver has fostered development of silver nanoparticles, which, however, present a potential health hazard. Here we present new silver coordination polymer networks with tailored physical and chemical properties as nanostructured coatings on metallic implant substrates. These compounds exhibited strong biofilm sugar-independent bactericidal activity on in vitro-grown biofilms and prevented murine Staphylococcus epidermidis implant infection in vivo with slow release of silver ions and limited transient leukocyte cytotoxicity. Furthermore, we describe the biochemical and molecular mechanisms of silver ion action by gene screening and by targeting cell metabolism of S. epidermidis at different levels. We demonstrate that silver ions inactivate enzymes by binding sulfhydryl (thiol) groups in amino acids and promote the release of iron with subsequent hydroxyl radical formation by an indirect mechanism likely mediated by reactive oxygen species. This is the first report investigating the global metabolic effects of silver in the context of a therapeutic application. We anticipate that the compounds presented here open a new treatment field with a high medical impact.

  15. Novel nano coordination polymer based synthesis of porous ZnO hexagonal nanodisk for higher gas sorption and photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Rakibuddin, M.; Ananthakrishnan, Rajakumar

    2016-01-01

    Zinc(II)-based nano co-ordination polymers (NCPs) are first prepared at room temperature from three different isomers of dihydroxysalophen (DHS) ligand with Zn(OAc)2·2H2O and 1,4-benzenedicarboxylic acid (BDC) in DMF solvent. Facile calcinations of [Zn (DHS) (BDC)]·nH2O (shortly denoted as Zn(II)-based NCP) at ambient conditions produces porous ZnO hexagonal nanodisks. Moreover, a novel approach has been introduced to observe the effect of ligand of the NCP on the physico-chemical properties of the as-synthesized ZnO. The porous ZnO nanodisks are characterized by FT-IR, PXRD, TEM, FESEM, EDX and BET analysis, and the results exhibit that they possess different sizes, surface areas and porosities. Nitrogen gas sorption capacity and photocatalytic activities of the as-prepared ZnO nanodisks are also checked, and it is noticed that they differ in these physico-chemical properties due to having different porosities and surface areas. A comparative study is also done with commercially available ZnO; interestingly, the commercial ZnO exhibited lower surface area, gas sorption and photocatalytic activity compared to the ZnO nanodisks. Hence, preparation of the ZnO through the NCP route and tuning their physico-chemical properties would offer new directions in synthesis of various nano metal oxides of unique properties.

  16. Synthesis, structures, luminescent and magnetic properties of four coordination polymers with the flexible 1,3-phenylenediacetate ligands

    NASA Astrophysics Data System (ADS)

    Gu, Jin-Zhong; Lv, Dong-Yu; Gao, Zhu-Qing; Liu, Jian-Zhao; Dou, Wei; Tang, Yu

    2011-03-01

    Four coordination polymers, [Zn(pda)(bpy)(H 2O)] n· nH 2O ( 1), [Cd(pda)(prz)(H 2O)] n ( 2), [Co 3( μ3-OH) 2(pda) 2(pyz)] n·2 nH 2O ( 3) and [Pr 2(pda) 3(H 2O) 2] n ( 4) (H 2pda=1,3-phenylendiacetic acid, bpy=4,4'-bipyridine, prz=piperazine and pyz=pyrazine) have been hydrothermally synthesized and characterized. Complex 1 is a 1D wheel-like chain structure, which is further extended into a 3D metal-organic supramolecular framework by H-bonds and π- π stacking interactions. Complex 2 is a 1D ladder-like chain structure, which is also further extended into a 3D metal-organic supramolecular framework by H-bonds. Complex 3 possess a 2D sheet structure with infrequent two pairs of double-helix chains. Complex 4 features a 3D structure. Both 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of complexes 3 and 4 exhibit antiferromagnetic interactions between the nearest metal ions, with C=9.99 and 3.43 cm 3 mol -1 K, and θ=-23.9 and -46.3 K, respectively.

  17. Polymer complexes: XLX. Novel supramolecular coordination modes of structure and bonding in polymeric hydrazone sulphadrugs uranyl complexes

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Diab, M. A.; El-Shehawy, M. S.; Moqbal, M.

    2010-01-01

    Novel five binuclear polymeric dioxouranium(VI) of azosulphadrugs [(azodrug substances) azobenzene sulphonamides] were prepared for the first time. The infrared spectra of the samples were recorded and their fundamental vibration wave number was obtained. The resulting polymeric uranyl complexes were characterized on the basis of their elemental analyses, conductance and spectral (IR, NMR, and electronic spectra) data. The ligation modes of the azosulphadrugs ligands towards uranyl(II) ions were critically assigned and addressed properly on the basis of their IR and their uranyl(II) complexes. The theoretical aspects are described in terms of the well-known theory of 5d-4f transitions. The coordination geometries and electronic structures are determined from a framework for the modeling of novel polymer complexes. The values of ν3 of the prepared complexes containing UO 22+ were successfully used to calculate the force constant, FUO (1n 10 -8 N/Å) and the bond length RUO of the U-O bond. Wilson's, matrix method, Badger's formula, and Jones and El-Sonbati equations were used to calculate the U-O bond distances from the values of the stretching and interaction force constants. The most probable correlations between U-O force constant to U-O bond distance were satisfactorily discussed in terms of "Badger's rule", "Jones" and "El-Sonbati equations".

  18. Self-assembled Nanoscale Coordination Polymers Carrying siRNAs and Cisplatin for Effective Treatment of Resistant Ovarian Cancer

    PubMed Central

    He, Chunbai; Liu, Demin; Lin, Wenbin

    2014-01-01

    Resistance to the chemotherapeutic agent cisplatin is a major limitation for the successful treatment of many cancers. Development of novel strategies to overcome intrinsic and acquired resistance to chemotherapy is of critical importance to effective treatment of ovarian cancer and other types of cancers. We have sought to re-sensitize resistant ovarian cancer cells to chemotherapy by co-delivering chemotherapeutics and pooled siRNAs targeting multi-drug resistance (MDR) genes using self-assembled nanoscale coordination polymers (NCPs). In this work, NCP-1 particles with trigger release properties were first constructed by linking cisplatin prodrug-based bisphosphonate bridging ligands with Zn2+ metal-connecting points and then coated with a cationic lipid layer, followed by the adsorption of pooled siRNAs targeting three MDR genes including survivin, Bcl-2, and P-glycoprotein via electrostatic interactions. The resulting NCP-1/siRNA particles promoted cellular uptake of cisplatin and siRNA and enabled efficient endosomal escape in cisplatin-resistant ovarian cancer cells. By down-regulating the expression of MDR genes, NCP-1/siRNAs enhanced the chemotherapeutic efficacy as indicated by cell viability assay, DNA ladder, and flow cytometry. Local administration of NCP-1/siRNAs effectively reduced tumor sizes of cisplatin-resistant SKOV-3 subcutaneous xenografts. This work shows that the NCP-1/siRNA platform holds great promise in enhancing chemotherapeutic efficacy for the effective treatment of drug-resistant cancers. PMID:25315138

  19. Large-scale preparation of indium-based infinite coordination polymer hierarchical nanostructures and their good capability for water treatment.

    PubMed

    Jin, Li-Na; Liu, Qing; Yang, Ying; Fu, Hong-Gang; Sun, Wei-Yin

    2014-07-15

    The removal of dyes in wastewater has been of much interest in the recent decades because dyes are stable, toxic and even potentially carcinogenic, and their release into environment causes serious environmental, aesthetical, and health problems. In the current work, indium-based coordination polymer particles (In-CPPs) have been fabricated via a facile solvothermal synthesis without any template or surfactant. In-CPPs are composed of hierarchical nanostructures assembled from abundant nanoplates with thickness of about 20 nm. Owing to their high BET surface area and pore volume, In-CPPs exhibit excellent adsorption capability for Congo red with a maximum capacity of 577 mg g(-1), which was higher than that of most materials reported to now. In-CPPS can also be outstanding adsorbents for removing other dyes such as acid chrome blue K, brilliant red GR and brilliant green. Furthermore, after calcinations in air In-CPPs can be converted to morphology-preserved porous In2O3 products which can detect NOx gas in air at room temperature.

  20. Synthesis, crystal structures, luminescence and catalytic properties of two d10 metal coordination polymers constructed from mixed ligands

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-xiao; Zhang, Ming-xi; Yu, Baoyi; Van Hecke, Kristof; Cui, Guang-hua

    2015-03-01

    Two new coordination polymers [Cd(bmb)(hmph)]n (1), {[Ag(bmb)]·H2btc}n (2) (bmb = 1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2hmph = homophthalic acid, H3btc = 1,3,5-benzenetetracarboxylic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction methods, IR spectroscopy, TGA, XRPD and elemental analysis. Complex 1 features a 3D threefold interpenetrating dia array with a 4-connected 66 topology. Complex 2 shows a 1D helix chain structure connected by L1 ligands, which is finally extended into a rarely 2D 4L2 supramolecular network via C-H⋯O hydrogen bond interactions. In addition, the luminescence and catalytic properties of the two complexes for the degradation of the methyl orange azo dye in a Fenton-like process were presented. The degradation efficiency of the methyl orange azo dye for 1 and 2 are 56% and 96%, respectively.

  1. Assembly of three new POM-based Ag(I) coordination polymers with antibacterial and photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Lu, Xin-Xin; Luo, Yu-Hui; Lu, Chen; Chen, Xin; Zhang, Hong

    2015-12-01

    Three new silver coordination polymers, namely, {Ag3(bpy)6[PW12O40]} (1), {Ag5(H2biim)2(Hbiim-NO2)2[PW12O40]} (2), {Ag7(pytz)4[PW12O40]} (3) (bpy=2,2‧-bipyridine, H2biim=2,2‧-biimidazole, pytz=4-(1H-tetrazol-5-yl)pyridine), have been synthesized under hydrothermal condition. Compound 1 shows a 3D supramolecular framework based on 0D moieties. Compound 2 exhibits an attractive 2D biologic screw axis. Compound 3 displays a 3D structure, which consists of Ag(I)···π interactions, π···π stacking and weak Ag···Ag interactions. It is noteworthy that nitration happens to compound 2 during the hydrothermal condition, which is quite rare. Through contrasting the antibacterial activities of gram negative and gram positive bacteria, we find compounds 1-3 have better antibacterial property in gram negative bacteria than gram positive bacteria. In addition, compounds 1-3 also exhibit efficiency of photocatalytic decomposition of organic dyes. Those compounds may be used as potential multifunctional materials in wastewater treatment, because they not only can kill bacteria but also degrade organic pollutants.

  2. A one-dimensional coordination polymer based on a di-Schiff base supported trinuclear CuII subunit.

    PubMed

    Zhang, Liangliang; Liu, Fuling; Yuan, Shuai; Wang, Xiaoyang; Sun, Di

    2012-04-01

    A novel one-dimensional Cu(II) coordination polymer, catena-poly[bis(μ(4)-3-{[2-(3-hydroxy-2-oxidobenzylidene)hydrazinylidene]methyl}benzene-1,2-diolato)dimethanoltricopper(II)], [Cu(3)(C(14)H(10)N(2)O(4))(2)(CH(3)OH)(2)](n), (I), was constructed with a di-Schiff base supported centrosymmetric trinuclear Cu(II) subunit. In the subunit, two peripheral symmetry-related Cu(II) cations have square-pyramidal CuNO(4) geometry and the central third Cu(II) cation lies on an inversion centre with octahedral CuN(2)O(4) geometry. In (I), each partially deprotonated di-Schiff base 3-{[2-(3-hydroxy-2-oxidobenzylidene)hydrazinylidene]methyl}benzene-1,2-diolate ligand (Hbcaz(3-)) acts as a heptadentate ligand to bind the Cu(II) centres into chains along the a axis. A centrosymmetric Cu(2)O(2) unit containing an asymmetrically bridging O atom, being axial at one Cu atom and equatorial at the other Cu atom, links the trinuclear Cu(II) subunit into a one-dimensional chain, which is reinforced by intramolecular phenol-methanol O-H...O and methanol-phenolate O-H...O hydrogen bonds. Interchain π-π stacking interactions between pyrocatechol units, with a distance of 3.5251 (18) Å, contribute to the stability of the crystal packing. PMID:22476144

  3. Highly selective and sensitive detection of metal ions and nitroaromatic compounds by an anionic europium(iii) coordination polymer.

    PubMed

    Feyisa Bogale, Raji; Ye, Junwei; Sun, Yuan; Sun, Tongxin; Zhang, Siqi; Rauf, Abdul; Hang, Cheng; Tian, Peng; Ning, Guiling

    2016-07-01

    A luminescent Eu(iii)-based coordination polymer, {[Eu(H2O)5(BTEC)][H(C5H6N2)]·3H2O} () has been synthesized under hydrothermal conditions using 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) as a linker. Compound possesses an anionic zig-zag chain constructed from the BTEC ligands and [EuO4(H2O)5] nodes. The protonated 4-aminopyridine groups as guests are located between chains. exhibits the characteristic sharp emission bands of Eu(3+) at 578, 593, 615, 652 and 693 nm upon excitation at 290 nm. The strong emission of could be quenched effectively by trace amounts of Fe(3+) ions even in the presence of other metal ions including Al(3+), Ca(2+), Cd(2+), Co(2+), Cr(3+), Cu(2+), Fe(2+), K(+), Mg(2+), Mn(2+), Pd(2+) and Zn(2+). Similarly, also exhibits superior selectivity and sensitivity towards 4-nitrophenol (4-NP) compared with other competing interfering analytes, such as 2,4,6-trinitrophenol, 2,6-dinitrotolune, 4-nitrotoluene, nitrobenzene, 1,3-dinitrobenzene, o-xylene, nitromethane, nitropropane, phenol, 4-bromophenol and bromobenzene, through a fluorescence quenching mechanism. The possible fluorescence quenching mechanisms are discussed. Moreover, could be used as a visual fluorescent test paper for selectively detecting trace amounts of Fe(3+) and 4-NP. PMID:27327158

  4. Design and synthesis of two luminescent Zn(II)-based coordination polymers with different structures regulated by different solvent system

    NASA Astrophysics Data System (ADS)

    Wu, Wei-Ping; Wen, Gui-Lin; Liao, Yi; Wang, Jun; Lu, Lu; Wu, Yu; Xie, Bin

    2016-08-01

    Two new coordination polymers (CPs) [Zn(HL)(H2O)]n (1) and [Zn3(L)2(H2O)2]n·(H2O)n (2), based on a multifunctional ligand combined carboxylate groups and a nitrogen donor group 5-(6-carboxypyridin-2-yl)isophthalic acid (H3L), have been synthesized under different solvent media and fully characterized by powder X-ray diffraction (PXRD), infrared (IR) spectra, elemental analyses (EA) and thermogravimetric analyses (TGA). Single-crystal X-ray diffraction analysis reveals that 1 shows 1D dimeric chain structure, while 2 gives a 3D dense packing framework. Topology analysis illustrates that 2 can be simplified as a 3-nodal net (4, 5, 6-connected net) with the point symbol of {44·62}{46·64}2{48·66·8}. In addition, solid state luminescent properties of two complexes have also been studied in detail, which may act as the potential optical materials.

  5. Study of proton conductivity of a 2D flexible MOF and a 1D coordination polymer at higher temperature.

    PubMed

    Sanda, Suresh; Biswas, Soumava; Konar, Sanjit

    2015-02-16

    We report the proton conduction properties of a 2D flexible MOF and a 1D coordination polymer having the molecular formulas {[Zn(C10H2O8)0.5(C10S2N2H8)]·5H2O]}n (1) and {[Zn(C10H2O8)0.5(C10S2N2H8)]·2H2O]}n (2), respectively. Compounds 1 and 2 show high conductivity values of 2.55 × 10(-7) and 4.39 × 10(-4) S cm(-1) at 80 °C and 95% RH. The conductivity value of compound 1 is in the range of those for previously reported flexible MOFs, and compound 2 shows the highest proton conductivity among the carboxylate-based 1D CPs. The dimensionality and the internal hydrogen bonding connectivity play a vital role in the resultant conductivity. Variable-temperature experiments of both compounds at high humidity reveal that the conductivity values increase with increasing temperature, whereas the variable humidity studies signify the influence of relative humidity on high-temperature proton conductivity. The time-dependent measurements for both compounds demonstrate their ability to retain conductivity up to 10 h.

  6. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    NASA Astrophysics Data System (ADS)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H. A. B. M. D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min

    2014-11-01

    Two lanthanide coordination polymers, namely, {[La(TTTA)(H2O)2]·2H2O}n (La-TTTA) and [Nd(TTTA)(H2O)2]·2H2O}n (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La3+ and Nd3+) with the flexible tripodal ligand 2,2‧,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H3TTTA). La-TTTA and Nd-TTTA are isostructural and both show three dimensional structures. La-TTTA and Nd-TTTA show good recognition of amine molecules via quenching the luminescent intensities in amines emulsions. They can also recognize Fe3+, Cu2+, Mg2+, Cr3+ and Co2+ ions with the quenching the peak around 361 nm when the compounds immersed in ionic solutions. The two compounds act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde and derivatives in high yields shortly due to the strong Lewis acidity and the possible open sites of the lanthanide ions.

  7. Highly selective and sensitive detection of metal ions and nitroaromatic compounds by an anionic europium(iii) coordination polymer.

    PubMed

    Feyisa Bogale, Raji; Ye, Junwei; Sun, Yuan; Sun, Tongxin; Zhang, Siqi; Rauf, Abdul; Hang, Cheng; Tian, Peng; Ning, Guiling

    2016-07-01

    A luminescent Eu(iii)-based coordination polymer, {[Eu(H2O)5(BTEC)][H(C5H6N2)]·3H2O} () has been synthesized under hydrothermal conditions using 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) as a linker. Compound possesses an anionic zig-zag chain constructed from the BTEC ligands and [EuO4(H2O)5] nodes. The protonated 4-aminopyridine groups as guests are located between chains. exhibits the characteristic sharp emission bands of Eu(3+) at 578, 593, 615, 652 and 693 nm upon excitation at 290 nm. The strong emission of could be quenched effectively by trace amounts of Fe(3+) ions even in the presence of other metal ions including Al(3+), Ca(2+), Cd(2+), Co(2+), Cr(3+), Cu(2+), Fe(2+), K(+), Mg(2+), Mn(2+), Pd(2+) and Zn(2+). Similarly, also exhibits superior selectivity and sensitivity towards 4-nitrophenol (4-NP) compared with other competing interfering analytes, such as 2,4,6-trinitrophenol, 2,6-dinitrotolune, 4-nitrotoluene, nitrobenzene, 1,3-dinitrobenzene, o-xylene, nitromethane, nitropropane, phenol, 4-bromophenol and bromobenzene, through a fluorescence quenching mechanism. The possible fluorescence quenching mechanisms are discussed. Moreover, could be used as a visual fluorescent test paper for selectively detecting trace amounts of Fe(3+) and 4-NP.

  8. Core-shell nanoscale coordination polymers combine chemotherapy and photodynamic therapy to potentiate checkpoint blockade cancer immunotherapy

    PubMed Central

    He, Chunbai; Duan, Xiaopin; Guo, Nining; Chan, Christina; Poon, Christopher; Weichselbaum, Ralph R.; Lin, Wenbin

    2016-01-01

    Advanced colorectal cancer is one of the deadliest cancers, with a 5-year survival rate of only 12% for patients with the metastatic disease. Checkpoint inhibitors, such as the antibodies inhibiting the PD-1/PD-L1 axis, are among the most promising immunotherapies for patients with advanced colon cancer, but their durable response rate remains low. We herein report the use of immunogenic nanoparticles to augment the antitumour efficacy of PD-L1 antibody-mediated cancer immunotherapy. Nanoscale coordination polymer (NCP) core-shell nanoparticles carry oxaliplatin in the core and the photosensitizer pyropheophorbide-lipid conjugate (pyrolipid) in the shell (NCP@pyrolipid) for effective chemotherapy and photodynamic therapy (PDT). Synergy between oxaliplatin and pyrolipid-induced PDT kills tumour cells and provokes an immune response, resulting in calreticulin exposure on the cell surface, antitumour vaccination and an abscopal effect. When combined with anti-PD-L1 therapy, NCP@pyrolipid mediates regression of both light-irradiated primary tumours and non-irradiated distant tumours by inducing a strong tumour-specific immune response. PMID:27530650

  9. Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

    NASA Astrophysics Data System (ADS)

    Uemura, Kazuhiro; Onishi, Fumiaki; Yamasaki, Yukari; Kita, Hidetoshi

    2009-10-01

    NO 2 containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO 2) and 2,5-dinitroterephthalate (bdc-(NO 2) 2), afford porous coordination polymers, {[Zn 2(bdc-NO 2) 2(dabco)]· solvents} n ( 2⊃ solvents) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]· solvents} n ( 3⊃ solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn 2 units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2⊃ solvents and 3⊃ solvents, a rectangle pore surrounded by eight Zn 2 corners contains two and four NO 2 moieties, respectively. Thermal gravimetry (TG) and X-ray powder diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me 2CO. Adsorption measurements reveal that dried 2 and 3 adsorb H 2O molecules to be {[Zn 2(bdc-NO 2) 2(dabco)]·4H 2O} n ( 2⊃4H 2O) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]·6H 2O} n ( 3⊃6H 2O), showing the pore hydrophilicity enhancement caused by NO 2 group introduction.

  10. Dimensional modulation and magnetic properties of triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates

    SciTech Connect

    Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin; Luan, Jian; Qu, Yun; Wang, Xiu-Li

    2014-04-01

    Five new metal–organic coordination polymers ([Cu{sub 3}(μ{sub 2}-OH){sub 2}(atrz){sub 2}(nph){sub 2}(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (1), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)]·2H{sub 2}O){sub n} (2), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)(H{sub 2}O)]·H{sub 2}O){sub n} (3), [Cu(dth){sub 0.5}(nph)(H{sub 2}O)]{sub n} (4) and [Cu(dth)(Hnip){sub 2}]{sub n} (5) [atrz=4-amino-1,2,4-triazole, dth=N,N'-di(4H-1,2,4-triazole)hexanamide, H{sub 2}nph=3-nitrophthalic acid, 1,2,4-H{sub 3}btc=1,2,4-benzenetricarboxylic acid and H{sub 2}nip=5-nitroisophthalic acid] were hydrothermally synthesized and structurally characterized. Polymer 1 shows a one-dimensional (1D) chain. Polymers 2 and 3 exhibit similar tetranuclear Cu{sup II}{sub 4} cluster-based three-dimensional (3D) frameworks with the same components. Polymer 4 possesses a 3D framework with a 4{sup 12}·6{sup 3}-pcu topology. Polymer 5 displays a 3D framework with a 4{sup 4}·6{sup 10}·8-mab topology. The magnetic properties of 1–4 were investigated. - Graphical abstract: Five triazole-based copper(II) polymers modulated by polycarboxylates were synthesized. Bis-triazole-bis-amide ligand and polycarboxylates play important roles in tuning dimensionality of polymers. Magnetic properties of polymers were investigated. - Highlights: • Five triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates were obtained. • The aromatic polycarboxylates have an important influence on the dimensionality of five polymers. • The magnetic properties of four polymers were investigated.

  11. C-H...Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu{sup I}Cu{sup II} coordination polymers

    SciTech Connect

    Shi Ling; Yang Ping; Huang Guang; Li Qian; Wang Ning; Wu Jianzhong; Yu Ying

    2011-07-15

    Two mixed-valence Cu{sup I}Cu{sup II} coordination polymers [Cu{sup I}Cu{sup II}(qdiol)ClL]{sub n} (qdiol{sup 2-}=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl{sub 2}, 1,4-dihydro-2,3-quinoxalinedione and L under the solvothermal condition. 1 and 2 are similar in composition, but differ remarkably in structure. The coordination modes of Cu{sup II}, qdiol{sup 2-} and L are identical in both complexes. But the Cu{sup I} ions are two- and three-coordinated, and the Cl{sup -} ions are terminal and bridging, in 1 and 2, respectively, which are relevant to the significantly different C-H...Cl hydrogen bonding pattern of bpy and phen. The temperature variable magnetic susceptibilities show that 1 is paramagnetic and 2 is weakly antiferromagnetic. The complex impedance spectroscopic studies indicate that both 1 and 2 are semiconductors and 2 is more conducting. - Graphical Abstract: Subtly different C-H...Cl bonding nature leads to diverse coordination modes and supramolecular networks, as well as physical properties of two Cu{sup I}Cu{sup II} coordination polymers with similar compositions. Highlights: > Two new Cu(I)-Cu(II) mixed-valence coordination polymers are obtained. > Environments of Cu(I) and Cl are different caused by C-H...Cl H-bonding. > Supramolecular networks are hence diverse. > Magnetic and semiconducting properties are influenced by the structures.

  12. Influence of the steric effect of flexible isomeric phenylenediacetic acids on the resultant lead(II) coordination polymers

    SciTech Connect

    Wu, Yunlong; Zhao, Yanqing; Yang, Guo-Ping Guo, Yanjun; Wang, Yao-Yu Shi, Qi-Zhen

    2015-03-15

    To study the steric effect of the flexible dicarboxylate ligands on the resultant formations of coordination polymers (CPs), four new Pb{sup II} CPs [Pb(1,2-pda)(H{sub 2}O)]{sub n} (1), [Pb(1,3-pda)]{sub n}·nH{sub 2}O (2), [Pb{sub 2}(1,4-pda){sub 2}(H{sub 2}O)]{sub n}·2nH{sub 2}O (3a and 3b) have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The X-ray crystallography study reveals that CP 1 is a two-dimensional (2D) 4-connected sql (4{sup 4}.6{sup 2}) network via the weak Pb···O interactions built on 1D chain-like structure. CP 2 crystallizes in orthorhombic system with chiral space group P2{sub 1}2{sub 1}2{sub 1}, showing a 4-connected sra (4{sup 2}.6{sup 3}.8) framework where a left-handed helical motif is formed by Pb{sup II} ions and trans-1,3-pda ligands. More interestingly, CPs 3a and 3b are two true 3D polymorphs and have the different morphology. Topologically, the framework of 3a exhibits a 4-connected lon 6{sup 6} motif, while that of 3b is a (4,6)-connected fsh (4{sup 3}.6{sup 3}){sub 2}(4{sup 6}.6{sup 6}.8{sup 3}) net. It is found that the three isomeric pda anions display the various coordination fashions in four CPs. The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Graphical abstract: Four new Pb{sup II}-based CPs have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Highlights: • Four Pb{sup II}-based coordination polymers were produced by phenylenediacetic acids. • The crystal and topological structures of the

  13. Self-Assembly, Structures, and Magnetic Properties of Ladder-Like Copper(II) Coordination Polymers

    NASA Astrophysics Data System (ADS)

    Min, Kil Sik; Suh, Myunghyun Paik

    2000-06-01

    Two novel ladder-like copper(II) compounds, [Cu2(histamine)2(C2O4)(ClO4)2] (1) and [Cu2(histamine)2(C2O4)(H2O)2(NO3)2] (2), are prepared. Compound 1 crystallizes in the triclinic space group Poverline1, with a=7.450(4) Å, b=7.519(7) Å, c=9.646(5) Å, α=85.78(7)°, β=88.60(4)°, γ=76.78(7)°, V=524.5(6) Å3, and Z=1 with R=0.0789 (all data). In 1, the dinuclear units of [Cu2(histamine)2(C2O4)]2+ are linked together by the perchlorate anions to form a ladder-like chain. The chains interact each other by the π-π stacking interactions via the imidazole groups. Compound 2 crystallizes in the triclinic space group Poverline1, with a=7.579(2) Å, b=8.133(1) Å, c=9.161(3) Å, α=77.06(2)°, β=89.23(2)°, γ=82.54(1)°, V=545.6(2) Å3, and Z=1 with R=0.0751 (all data). In 2, each dinuclear unit [Cu2(histamine)2(C2O4)]2+ is coordinated with a nitrate anion and a water molecule, and they are held together by the hydrogen bonding interactions to form a ladder-like chain. The magnetic susceptibility data of 1 and 2 measured in 2-300 K provide the magnetic parameters, g=2.08, J=-166 cm-1, J‧=6.46 cm-1, ρ=0.0026, Nα=155×10-6 cm3 mol-1, and R=1.03×10-3 (g=2.05, J=-162 cm-1, J‧=10.5 cm-1, ρ=0.0029, and R=2.95×10-3 with the fixed value of Nα=120×10-6 cm3 mol-1) for 1 and g=2.00, J=-158 cm-1, J‧=26.5 cm-1, ρ=0.0020, Nα=136×10-6 cm3 mol-1, and R=7.31×10-4 (g=2.01, J=-157 cm-1, J‧=25.0 cm-1, ρ=0.0021, and R=1.32×10-3 with the fixed value of Nα=120×10-6 cm3 mol-1) for 2. These indicate that very strong antiferromagnetic interactions occur along the rungs of the ladder via the oxalate bridge and weak ferromagnetic interactions along the chains.

  14. Microwave-assisted ionothermal synthesis of a water-stable Eu-coordination polymer: a Ba(2+) ion detector and fluorescence thermometer.

    PubMed

    Wang, Ze-Ping; Hu, Bing; Qi, Xing-Hui; Shen, Nan-Nan; Huang, Xiao-Ying

    2016-06-01

    A water-stable Eu-coordination polymer (CP), namely [HMIm]Eu(DHBDC)2 (1) (HMIm = 1-hexyl-3-methylimidazolium; H2DHBDC = 2,5-dihydroxytelephthalic acid), was obtained using ionothermal synthesis. 1 represents the first coordination polymer capable of qualitative and quantitative detection of Ba(2+) in aqueous solutions with a fluorescent enhancement that is visible to the human eye, which can be ascribed to the formation of fluorescent compound Ba(DHBDC) (2) during the detection process. Temperature-dependent photoluminescence (PL) makes 1 a potential material for a fluorescence thermometer. Furthermore, the detection process for Ba(2+) using 1 turns the one-PL transition fluorescence thermometer into a two-PL transition fluorescence thermometer, increasing the accuracy of the fluorescence thermometer.

  15. Design and synthesis of new 1D and 2D R-isophthalic acid-based coordination polymers (R = hydrogen or bromine).

    PubMed

    Zhang, Ren; Gong, Qihan; Emge, Thomas J; Banerjee, Debasis; Li, Jing

    2013-01-01

    Three new R-isophthalic acid-based (R = H or Br) coordination polymers have been designed and synthesized. By changing the N-containing ligand in the system, we are able to tune the dimensionality of coordination polymers from one-dimension (1D) to two-dimensions (2D) with the same basic building unit. Also, different metal ions can be incorporated into the same structures. Compound 1 [Cu(bipa)(py)2]·0.5(H2O) (H2bipa = 5-bromoisophthalic acid; py = pyridine) and compound 2 [Co(bipa)(py)2] are 1D chain structures. Compound 3 [Cu8(ipa)8(bpe)8]·2(bpe)·4(H2O) (bpe=1,2-bis(4-pyridyl)ethane) is a 2D layered structure.

  16. Microwave-assisted ionothermal synthesis of a water-stable Eu-coordination polymer: a Ba(2+) ion detector and fluorescence thermometer.

    PubMed

    Wang, Ze-Ping; Hu, Bing; Qi, Xing-Hui; Shen, Nan-Nan; Huang, Xiao-Ying

    2016-06-01

    A water-stable Eu-coordination polymer (CP), namely [HMIm]Eu(DHBDC)2 (1) (HMIm = 1-hexyl-3-methylimidazolium; H2DHBDC = 2,5-dihydroxytelephthalic acid), was obtained using ionothermal synthesis. 1 represents the first coordination polymer capable of qualitative and quantitative detection of Ba(2+) in aqueous solutions with a fluorescent enhancement that is visible to the human eye, which can be ascribed to the formation of fluorescent compound Ba(DHBDC) (2) during the detection process. Temperature-dependent photoluminescence (PL) makes 1 a potential material for a fluorescence thermometer. Furthermore, the detection process for Ba(2+) using 1 turns the one-PL transition fluorescence thermometer into a two-PL transition fluorescence thermometer, increasing the accuracy of the fluorescence thermometer. PMID:27110830

  17. Series of coordination polymers based on 4-(5-sulfo-quinolin-8-yloxy) phthalate and bipyridinyl coligands: Structure diversity and properties

    NASA Astrophysics Data System (ADS)

    Feng, Xun; Liu, Jing; Li, Jin; Ma, Lu-Fang; Wang, Li-Ya; Ng, Seik-Weng; Qin, Guo-Zhan

    2015-10-01

    Reactions between later metal salts and conjugational N-hetrocyclic sulfonate/ carboxylic acid under the presence of bipyridyl auxiliary ligands afforded a series of manganese, nickel, zinc, silver, cadmium coordination polymers bearing with phenyl pendant arm attached to quinoline skeletons, and they have been characterized by elements analysis, thermogravimetry, infrared spectroscopy and single-crystal X-ray diffraction studying. The series of polymers show interesting structural diversity in coordination environment, dimensions and topologies. They are all built from 2-D networks constructed from metal cluster through sulfonate or carboxylate groups, as the secondary building unit (SBU). The thermalgravimetric analyses show that they display framework stabilities in solid state. Variable-temperature magnetic susceptibility studies reveal the existence of antiferromagnetic interactions between adjacent Mn (II) ions in 1, and ferromagnetic interactions between Ni(II) ions for 2, respectively. The photo-luminescence properties of 3-5 have also been investigated systemically.

  18. Extending the lanthanide-terephthalate system: Isolation of an unprecedented Tb(III)-based coordination polymer with high potential porosity and luminescence properties

    NASA Astrophysics Data System (ADS)

    Le Natur, François; Calvez, Guillaume; Freslon, Stéphane; Daiguebonne, Carole; Bernot, Kevin; Guillou, Olivier

    2015-04-01

    A novel coordination polymer with chemical formula {[Tb(bdc)1.5(H2O)]ṡ(DMF)(H2O)}∞ (1) has been synthesized by reaction between 1,4-benzene-dicarboxylic acid (H2bdc) and di-cationic hexanuclear entity [Tb6O(OH)8(NO3)6(H2O)12]2+ in an ethylene glycol (EG)/N,N-dimethylformamide (DMF) mixture. This compound has been obtained as single crystals by slow evaporation in air at room temperature. If the hexanuclear entity is destroyed during the reaction, the coordination polymer that is obtained is original and presents promising potential micro-porosity and luminescent properties. It crystallizes in the monoclinic system, space group C12/c1 (No. 15) with the cell parameters a = 23.7540(1) Å, b = 10.5390(4) Å, c = 19.7580(3) Å, β = 125.8100(1)° and Z = 8.

  19. Time-resolved probes and oxidase-based biosensors using terbium(III)-guanosine monophosphate-mercury(II) coordination polymer nanoparticles.

    PubMed

    Zhang, Min; Qu, Zhi-bei; Han, Chun-Min; Lu, Ling-Fei; Li, Yan-Yun; Zhou, Tianshu; Shi, Guoyue

    2014-11-01

    A novel lanthanide coordination polymer nanoparticle (LCPN)-based ternary complex was synthesized via the self-assembly of a terbium ion (Tb(3+)) with a nucleotide (GMP) and a mercury ion (Hg(2+)) in aqueous solution. The as-prepared LCPN-based ternary complex (Tb-GMP-Hg) can be applied to the development of time-resolved luminescence assays and oxidase-based biosensors.

  20. A new Kagomé lattice coordination polymer based on bismuth and pyridine-2,5-dicarboxylate: structure and photoluminescent properties.

    PubMed

    Wibowo, Arief C; Smith, Mark D; zur Loye, Hans-Conrad

    2011-07-14

    A new Kagomé lattice topology assembled from ML(4) metal-organic polyhedra prepared using bismuth nitrate and pyridine-2,5-dicarboxylate has been obtained via a solvo-thermal reaction. Bi(pydc)(2)·(H(3)O(+))(H(2)O)(0.83) is, to the best of our knowledge, the first example of a bismuth-based coordination polymer to form with a Kagomé topology. Its structure and photoluminescence properties are reported.

  1. Ammonium-crown ether supramolecular cation-templated assembly of an unprecedented heterobicluster-metal coordination polymer with enhanced NLO properties.

    PubMed

    Zhang, Jinfang; Jia, Ding; Humphrey, Mark G; Meng, Suci; Zaworotko, Michael J; Cifuentes, Marie P; Zhang, Chi

    2016-03-01

    An ammonium-crown ether host-guest supramolecular cation-templated synthetic methodology has been developed to construct a structurally unprecedented heterobicluster-metal coordination polymer (HCM-CP 1) based on tetranuclear clusters [WS4Cu3](+) with different connection environments, pentanuclear clusters [WS4Cu4](2+), and Cu(+) building metal ions. HCM-CP 1 exhibits enhanced NLO properties, which may be ascribed to the incorporation of diverse building cluster components.

  2. Ammonium-crown ether supramolecular cation-templated assembly of an unprecedented heterobicluster-metal coordination polymer with enhanced NLO properties.

    PubMed

    Zhang, Jinfang; Jia, Ding; Humphrey, Mark G; Meng, Suci; Zaworotko, Michael J; Cifuentes, Marie P; Zhang, Chi

    2016-03-01

    An ammonium-crown ether host-guest supramolecular cation-templated synthetic methodology has been developed to construct a structurally unprecedented heterobicluster-metal coordination polymer (HCM-CP 1) based on tetranuclear clusters [WS4Cu3](+) with different connection environments, pentanuclear clusters [WS4Cu4](2+), and Cu(+) building metal ions. HCM-CP 1 exhibits enhanced NLO properties, which may be ascribed to the incorporation of diverse building cluster components. PMID:26864604

  3. Secondary ligand-directed assembly of Co(II) coordination polymers based on a pyridine carboxylate ligand

    SciTech Connect

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni; Xu, Xiao-Wei; Feng, Yun-Long

    2014-07-01

    To investigate the influence of hydrogen bonds and secondary ligands on the structures and properties of the resulting frameworks, five new Co(II) compounds have been synthesized by the reactions of Co(II) salts and 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL) with four rationally selected dicarboxylic acid ligands. Without secondary ligand, we got one compound [CoL{sub 2}(H{sub 2}O){sub 2}]{sub n}·2nH{sub 2}O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H{sub 2}adbc), terephthalic acid (H{sub 2}tpa), thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) and 1,4-benzenedithioacetic acid (H{sub 2}bdtc), four 3D structures [Co{sub 2}L{sub 2}(adbc)]{sub n}·nH{sub 2}O (2), [Co{sub 2}L{sub 2}(tpa)]{sub n} (3), [Co{sub 2}L{sub 2}(tdc)]{sub n} (4), [Co{sub 2}L{sub 2}(bdtc)(H{sub 2}O)]{sub n} (5) were obtained, respectively. It can be observed from the architectures of 1–5 that hydrogen bonds and secondary ligands both have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. The XRPD, TGA data of title polymers and the magnetic properties for 2 and 5 have also been investigated. - Graphical abstract: The structural differences show that the ancillary ligands have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. - Highlights: • Five new Co(II) coordination polymers have been synthesized by solvothermal reactions based on 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL). • The long-flexible ligand (HL) is a good candidate to produce interpenetrating architectures. • The secondary dicarboxylic acid ligands play important roles in the spatial connective fashions and the formation of various dimensional compounds. • The magnetism studies show that both 2 and 5 exhibit antiferromagnetic interactions.

  4. Synthesis and characterization of multifunctional coordination polymer of the type [CuxNi1-x(dedb)·2H2O]n

    NASA Astrophysics Data System (ADS)

    Singh, Deepshikha; Kushwaha, Anita; Banerjee, A.; Prasad, R. L.

    2015-07-01

    New series of multifunctional homometallic and heterobimetallic coordination polymers of the type [CuxNi1-x(dedb)·2H2O]n {where dedb = dianion of 2,5-dichloro-3,6-bis(ethylamino)-1,4-benzoquinone (1); x = 1, (2); 0 (3); 0.5 (4); 0.25 (5); 0.125 (6); 0.0625 (7) and n = degree of polymerization} have been synthesized and characterized by Powder X-ray diffraction, IR, UV-visible and ESR spectroscopic techniques. Variable temperature susceptibility measurement indicates presence of strong ferromagnetic interaction. The effects of copper doping on thermal, magnetic and conducting properties of these polymers have been investigated in this communication. A rare co-existence of ferromagnetism as well as electrical conductivity has been observed in these polymers.

  5. Immobilization of ALA-Zn(II) Coordination Polymer Pro-photosensitizers on Magnetite Colloidal Supraparticles for Target Photodynamic Therapy of Bladder Cancer.

    PubMed

    Tan, Jing; Sun, Chuanyu; Xu, Ke; Wang, Changchun; Guo, Jia

    2015-12-16

    5-Aminolevulinic acid (ALA) is a widely used photodynamic therapy (PDT) prodrug in the clinic. It can be metalized to the photosensitizer PpIX, which produces toxic singlet oxygen to kill cancer cells upon visible light irradiation. Herein, a core/shell-structured vehicle is designed to comprise magnetite colloidal supraparticles (MCSPs) as cores and ALA-Zn(II) coordination polymers as shells (Fe3O4@ALA-Zn(II) ) for target pro-photosensitizer delivery. The coordination polymers with 2D layered structures are locally deposited on the MCSPs by the complexation of the ALA and Zn(II) ions, and are readily controlled by varying the feed precursors and reaction temperatures. The maximum conjugated ALA amount is up to 17%. The Fe3O4@ALA-Zn(II) microspheres exhibit pH-sensitive release of ALA in acidic environment and rapid magnetic responsiveness. Cytotoxicity results demonstrate that Fe3O4@ALA-Zn(II) shows a significant inhibitory effect to T24 cells and is nontoxic to 293T normal cells as exposed to the 630 nm visible light for a very short time, which may due to the selective accumulation of ALA-induced PpIX in T24 cancer cells. Compared to the ALA used alone, the coordination polymer form is more efficient because of the bioactivity of incorporated Zn ions despite underlying the same apoptosis mechanism as ALA agent.

  6. Series of coordination polymers based on 4-(5-sulfo-quinolin-8-yloxy) phthalate and bipyridinyl coligands: Structure diversity and properties

    SciTech Connect

    Feng, Xun; Liu, Jing; Li, Jin; Ma, Lu-Fang; Wang, Li-Ya; Ng, Seik-Weng; Qin, Guo-Zhan

    2015-10-15

    Reactions between later metal salts and conjugational N-hetrocyclic sulfonate/ carboxylic acid under the presence of bipyridyl auxiliary ligands afforded a series of manganese, nickel, zinc, silver, cadmium coordination polymers bearing with phenyl pendant arm attached to quinoline skeletons, and they have been characterized by elements analysis, thermogravimetry, infrared spectroscopy and single-crystal X-ray diffraction studying. The series of polymers show interesting structural diversity in coordination environment, dimensions and topologies. They are all built from 2-D networks constructed from metal cluster through sulfonate or carboxylate groups, as the secondary building unit (SBU). The thermalgravimetric analyses show that they display framework stabilities in solid state. Variable-temperature magnetic susceptibility studies reveal the existence of antiferromagnetic interactions between adjacent Mn (II) ions in 1, and ferromagnetic interactions between Ni(II) ions for 2, respectively. The photo-luminescence properties of 3-5 have also been investigated systemically. - Highlights: • A series of coordination polymers based on later transition metal ions have been obtained. • They contain conjugational N-hetrocyclic sulfonate-carboxylic acid and bipyridyl auxiliary ligands. • They have been characterized systemically. • They exhibit structure diversity and interesting properties.

  7. Metallogels derived from silver coordination polymers of C3-symmetric tris(pyridylamide) tripodal ligands: synthesis of Ag nanoparticles and catalysis.

    PubMed

    Paul, Mithun; Sarkar, Koushik; Dastidar, Parthasarathi

    2015-01-01

    By applying a recently developed crystal engineering rationale, four C3 symmetric tris(pyridylamide) ligands namely 1,3,5-tris(nicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(isonicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(nicotinamidomethyl)-2,4,6-trimethylbenzene, and 1,3,5-tris(isonicotinamidomethyl)-2,4,6-trimethylbenzene, which contain potential hydrogen-bonding sites, were designed and synthesized for generating Ag(I) coordination polymers and coordination-polymer-based gels. The coordination polymers thus obtained were characterized by single-crystal X-ray diffraction. The silver metallogels were characterized by transmission electron microscopy (TEM) and dynamic rheology. Upon exposure to visible light, these silver metallogels produced silver nanoparticles (AgNPs), which were characterized by TEM, powder X-ray diffraction, energy dispersive X-ray and X-ray photoelectron spectroscopy. These NPs were found to be effectively catalyzed the reduction of 4-nitrophenolate to 4-aminophenolate without the use of any exogenous reducing agent.

  8. A two-dimensional layered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating mixed multidentate N- and O-donor ligands.

    PubMed

    Huang, Qiu-Ying; Su, Ming-Yang; Meng, Xiang-Ru

    2015-06-01

    The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{μ2-1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κ(2)N(3):N(4)}(μ4-butanedioato-κ(4)O(1):O(1'):O(4):O(4'))(μ2-butanedioato-κ(2)O(1):O(4))dicadmium], [Cd(C4H4O4)(C9H8N6)]n, each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) ligands. Cd(II) ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.

  9. Synthesis and Structure of a New Copper(II) Coordination Polymer Alternately Bridged by Oxamido and Carboxylate Groups: Evaluation of DNA/BSA Binding and Cytotoxic Activities.

    PubMed

    Jin, Xiao-Ting; Zheng, Kang; Li, Yan-Tuan; Wu, Zhi-Yong; Yan, Cui-Wei

    2015-08-01

    A new one-dimensional (1D) copper(II) coordination polymer {[Cu2 (dmaepox)(dabt)](NO3) · 0.5 H2 O}n , where H3 dmaepox and dabt denote N-benzoato-N'-(3-methylaminopropyl)oxamide and 2,2'-diamino-4,4'-bithiazole, respectively, was synthesized and characterized by single-crystal X-ray diffraction and other methods. The crystal structure analysis revealed that the two copper(II) ions are bridged alternately by cis-oxamido and carboxylato groups to form a 1-D coordination polymer with the corresponding Cu · · · Cu separations of 5.1946(19) and 5.038(2) Å. There is a three-dimensional supramolecular structure constructed by hydrogen bonding and π-π stacking interactions in the crystal. The reactivity towards herring sperm DNA (HS-DNA) and bovine serum albumin (BSA) indicated that the copper(II) polymer can interact with the DNA in the mode of intercalation, and bind to BSA responsible for quenching of tryptophan fluorescence by the static quenching mechanism. The in vitro cytotoxicity suggested that the copper(II) polymer exhibits cytotoxic effects against the selected tumor cell lines.

  10. One-dimensional Cu(II) coordination polymers containing C2h-symmetric 1,1':4',1''-terphenyl-3,3'-dicarboxylate linkers.

    PubMed

    Kim, Hyun Chul; Gu, Ja Min; Huh, Seong; Yo, Chul Hyun; Kim, Youngmee

    2015-10-01

    Two new one-dimensional Cu(II) coordination polymers (CPs) containing the C2h-symmetric terphenyl-based dicarboxylate linker 1,1':4',1''-terphenyl-3,3'-dicarboxylate (3,3'-TPDC), namely catena-poly[[bis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(4)O,O':O'':O'''] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), and catena-poly[[aquabis(dimethylamine-κN)copper(II)]-μ-1,1':4',1''-terphenyl-3,3'-dicarboxylato-κ(2)O(3):O(3')] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3'-TPDC bridging ligands coordinate the Cu(II) ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).

  11. Vapochromic luminescence and flexibility control of porous coordination polymers by substitution of luminescent multinuclear Cu(I) cluster nodes.

    PubMed

    Hayashi, Takahiro; Kobayashi, Atsushi; Ohara, Hiroki; Yoshida, Masaki; Matsumoto, Takeshi; Chang, Ho-Chol; Kato, Masako

    2015-09-21

    Two luminescent porous coordination polymers (PCPs), i.e., [Cu2(μ2-I)2ctpyz]n and [Cu4(μ3-I)4ctpyz]n (Cu2 and Cu4, respectively; ctpyz = cis-1,3,5-cyclohexanetriyl-2,2',2″-tripyrazine), were successfully synthesized and characterized by single-crystal X-ray diffraction and luminescence spectroscopic measurements. Cu2 consists of rhombus-type dinuclear {Cu2I2} cores bridged by ctpyz ligands, while Cu4 is constructed of cubane-type tetranuclear {Cu4I4} cores bridged by ctpyz ligands. The void fraction of Cu4 is estimated to be 48.0%, which is significantly larger than that of Cu2 (19.9%). Under UV irradiation, both PCPs exhibit red luminescence at room temperature in the solid state (λem values of 660 and 614 nm for Cu2 and Cu4, respectively). Although the phosphorescence of Cu2 does not change upon removal and/or adsorption of EtOH solvent molecules in the porous channels, the solid-state emission maximum of Cu4 red-shifts by 36 nm (λem = 650 nm) upon the removal of the adsorbed benzonitrile (PhCN) molecules from the porous channels (and vice versa). This large difference in the vapochromic behavior of Cu2 and Cu4 is closely related to the framework flexibility. The framework of Cu2 is sufficiently rigid to retain the porous structure without solvated EtOH molecules, whereas the porous structure of Cu4 collapses easily after removal of the adsorbed PhCN molecules to form a nonporous amorphous phase. The original vapor-adsorbed porous structure of Cu4 is regenerated by exposure of the amorphous solid to not only PhCN vapor but also tetrahydrofuran, acetone, ethyl acetate, and N,N-dimethylformamide vapors. The Cu4 structures with the various adsorbed solvents showed almost the same emission maxima as the original PhCN-adsorbed Cu4, except for DMF-adsorbed Cu4, which showed no luminescence probably because of weak coordination of the DMF vapor molecules to the Cu(I) centers of the tetranuclear {Cu4I4} core.

  12. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    SciTech Connect

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min

    2014-11-15

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (La-TTTA) and [Nd(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La{sup 3+} and Nd{sup 3+}) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H{sub 3}TTTA). La-TTTA and Nd-TTTA are isostructural and both show three dimensional structures. La-TTTA and Nd-TTTA show good recognition of amine molecules via quenching the luminescent intensities in amines emulsions. They can also recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions with the quenching the peak around 361 nm when the compounds immersed in ionic solutions. The two compounds act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde and derivatives in high yields shortly due to the strong Lewis acidity and the possible open sites of the lanthanide ions. - Graphical abstract: We have synthesized two isostructural 3D compounds based on H{sub 3}TTTA. They are chemical sensor of amine solvents and cations. They have higher yields and TOFs to catalyze cyanosilylation reactions. - Highlights: • The compounds show recognition of amine molecules via quenching luminescent intensities. • The compounds recognize Fe{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields.

  13. A 3D Heterometallic Coordination Polymer Constructed by Trimeric {NiDy2} Single-Molecule Magnet Units.

    PubMed

    Zhang, Shaowei; Li, Han; Duan, Eryue; Han, Zongsu; Li, Leilei; Tang, Jinkui; Shi, Wei; Cheng, Peng

    2016-02-01

    The solvothermal reaction of DyCl3·6H2O, Ni(NO3)2·6H2O, and H4abtc ligands (H4abtc = 3,3',5,5'-azobenzene-tetracarboxylic acid) in the mixed DMF/H2O solvents (DMF = N,N-dimethylformamide) produced a three-dimensional (3D) Ni(II)-Dy(III) heterometallic coordination polymer (HCP) formulated as {[NH2(CH3)2]2[NiDy2(HCOO)2(abtc)2]}n (1). In 1, Dy(III) and Ni(II) ions interconnect through carboxylic O donors of abtc(4-) ligands to generate a linear trimer "Hourglass"-type {NiDy2} cluster, and the adjacent trinuclear {NiDy2} units are bridged by HCOO(-) groups to give a 1D "ladder" chain, which is further bridged by abtc(4-) ligands to form a new topology and named as "zsw3". Alternating-current magnetic susceptibility results indicate that 1 exhibits frequency-dependent out-of-phase signals with two relaxation processes, which suggests that it shows single-molecule magnet (SMM) behavior and represents the first example by using an SMM cluster as the building block to create a 3D Ni-Ln HCP, to the best of our knowledge. The energy barriers for 1 under a 1000 Oe applied direct current magnetic field are estimated from Arrhenius plots to be 40 and 42 K at higher and lower frequencies, respectively. Additionally, the crystalline structure of 1 could be stable to at least 310 °C, supported by thermogravimetric analyses and in situ variable-temperature powder X-ray diffraction patterns.

  14. Seven 3d-4f coordination polymers of macrocyclic oxamide with polycarboxylates: Syntheses, crystal structures and magnetic properties

    NASA Astrophysics Data System (ADS)

    Xin, Na; Sun, Ya-Qiu; Zheng, Yan-Feng; Xu, Yan-Yan; Gao, Dong-Zhao; Zhang, Guo-Ying

    2016-11-01

    Seven new 3d-4f heterometallic coordination polymers, [Ln(CuL)2(Hbtca)(btca)(H2O)]·2H2O (Ln = TbIII1, PrIII2, SmIII3, EuIII4, YbIII5), [Nd(NiL)(nip)(Rnip)]·0·25H2O·0.25CH3OH (R= 0.6CH3, 0.4H) 6 and [Nd2(NiL)(nip)3(H2O)]·2H2O 7(CuL or NiL, H2L = 2, 3-dioxo-5, 6, 14, 15-dibenzo-1, 4, 8, 12-tetraazacyclo-pentadeca-7, 13-dien; H2btca = benzotriazole-5-carboxylic acid; H2nip = 5-nitroisophthalic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1-5 exhibit a double-strand meso-helical chain structures formed by [LnIIICuII2] units via the oxamide and benzotriazole-5-carboxylate bridges, while complex 6 exhibits a four-strand meso-helical chain formed by NdNi unit via the oxamide and 5-nitroisophthalate bridges. Complex 7 consists of a 2D layer framework formed by four-strand meso-helical chain via the nip2- bridges. Moreover, the magnetic properties of them were investigated, and the best-fit analysis of χMT versus T show that the anisotropic contribution of Ln(III) ions (arising from the spin-orbit coupling or the crystal field perturbation) dominates (weak exchange limit) in these complexes(for 3, λ = 214.6 cm-1, zj' = -0.33 cm-1, gav = 1.94; for 5, Δ = 6.98 cm-1, zj' = 1.53 cm-1, gav = 1.85).

  15. Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer.

    PubMed

    Guillet, Jesse L; Bhowmick, Indrani; Shores, Matthew P; Daley, Christopher J A; Gembicky, Milan; Golen, James A; Rheingold, Arnold L; Doerrer, Linda H

    2016-08-15

    A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K.

  16. Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer.

    PubMed

    Guillet, Jesse L; Bhowmick, Indrani; Shores, Matthew P; Daley, Christopher J A; Gembicky, Milan; Golen, James A; Rheingold, Arnold L; Doerrer, Linda H

    2016-08-15

    A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K. PMID:27486841

  17. Entangled coordination polymers with mixed N- and O-donor organic linkers: a case of module-matching priority.

    PubMed

    Han, Li-Wei; Gong, Yun; Lin, Zu-Jin; Lü, Jian; Cao, Rong

    2012-04-14

    A series of four coordination polymers showing entangled architectures based on cobalt and mixed N-donor/O-donor ligands, namely [Co(4,4'-BPIPA)(TP)]·2DMF (1), [Co(4,4'-BPIPA)(2,6-NDC)(DMF)]·DMF (2), [Co(4,4'-BPIPA)(2,6-NDC)]·2DMF (3) and [Co(4,4'-BPIPA)(4,4'-BPDC)]·2DMF (4) (4,4'-BPIPA = N,N'-bis-4-pyridinyl-isophthalamide, TP = terephthalic acid, 2,6-NDC = 2,6-naphthalenedicarboxylic acid, 4,4'-BPDC = 4,4'-biphenyldicarboxylic acid), have been synthesized under solvothermal conditions. Complex 1, containing 4,4'-BPIPA and relatively short dicarboxylate ligands (TP), exhibits two-dimensional (2D) two-fold interpenetration of double wavy 4(4)-sql nets. Complex 2 displays interesting 2D→3D parallel polycatenation of undulated 2D 4(4)-sql layers built by 4,4'-BPIPA and moderate dicarboxylate ligands (2,6-NDC). Complexes 3 and 4, although constructed of dicarboxylate ligands with different lengths (moderate 2,6-NDC and long 4,4'-BPDC), possess similar 3-fold interpenetration of identical self-catenated single nets with 6(5)·8-mok topologies. It has been found that the length of the dicarboxylate ligands plays a key role of module-matching in the self-assemblies of complexes 1-4. Moreover, the effect of the conformations of 4,4'-BPIPA, which can be controlled by tuning reaction temperatures, is also discussed.

  18. Zn(II) coordination polymers with flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

    NASA Astrophysics Data System (ADS)

    Li, Lin; Liu, Chong-Bo; Yang, Gao-Shan; Xiong, Zhi-Qiang; Liu, Hong; Wen, Hui-Liang

    2015-11-01

    Hydrothermal reactions of 2,2‧-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H2L) and zinc ions in the presence of N-donor ancillary ligands afford four novel coordination polymers, namely, [Zn2(μ2-OH)(μ4-O)0.5(L)]·0.5H2O (1), [Zn(L)(2,2‧-bipy)(H2O)] (2), [Zn3(L)3(phen)2]·H2O (3) and [Zn2(L)2(4,4‧-bipy)] (4) (2,2‧-bipy=2,2‧-bipyridine; 4,4‧-bipy=4,4‧-bipyridine; phen=1,10-phenanthroline). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complex 1 shows a 3-D clover framework consisting of [Zn4(μ4-O)(μ2-OH)2]4+ clusters, and exhibits a novel (3,8)-connected topological net with the Schläfli symbol of {3·4·5}2{34·44·52·66·710·82}, and contains double-stranded and two kinds of meso-helices. 2 displays a helical chain structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with meso-helix chains. 3 displays a 2-D {44·62} parallelogram structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with single-stranded helical chains. 4 shows a 2-D {44·62} square structure with left- and right-handed helical chains. Moreover, the luminescent properties of 1-4 have been investigated.

  19. Absorption of CO2 and CS2 into the Hofmann-type porous coordination polymer: electrostatic versus dispersion interactions.

    PubMed

    Deshmukh, Milind Madhusudan; Ohba, Masaaki; Kitagawa, Susumu; Sakaki, Shigeyoshi

    2013-03-27

    Absorption of CO2 and CS2 molecules into the Hofmann-type three-dimensional porous coordination polymer (PCP) {Fe(Pz)[Pt(CN)4]}n (Pz = pyrazine) was theoretically explored with the ONIOM(MP2.5 or SCS-MP2:DFT) method, where the M06-2X functional was employed in the DFT calculations. The binding energies of CS2 and CO2 were evaluated to be -17.3 and -5.2 kcal mol(-1), respectively, at the ONIOM(MP2.5:M06-2X) level and -16.9 and -4.4 kcal mol(-1) at the ONIOM(SCS-MP2:M06-2X) level. It is concluded that CS2 is strongly absorbed in this PCP but CO2 is only weakly absorbed. The absorption positions of these two molecules are completely different: CO2 is located between two Pt atoms, whereas one S atom of CS2 is located between two Pz ligands and the other S atom is between two Pt atoms. The optimized position of CS2 agrees with the experimentally reported X-ray structure. To elucidate the reasons for these differences, we performed an energy decomposition analysis and found that (i) both the large binding energy and the absorption position of CS2 arise from a large dispersion interaction between CS2 and the PCP, (ii) the absorption position of CO2 is mainly determined by the electrostatic interaction between CO2 and the Pt moiety, and (iii) the small binding energy of CO2 comes from the weak dispersion interaction between CO2 and the PCP. Important molecular properties relating to the dispersion and electrostatic interactions, which are useful for understanding and predicting gas absorption into PCPs, are discussed in detail.

  20. Photo-induced DNA cleavage activity and remarkable photocytotoxicity of lanthanide(III) complexes of a polypyridyl ligand.

    PubMed

    Hussain, Akhtar; Gadadhar, Sudarshan; Goswami, Tridib K; Karande, Anjali A; Chakravarty, Akhil R

    2012-01-21

    Lanthanide(III) complexes [Ln(pyphen)(acac)(2)(NO(3))] (1, 2), [Ln(pydppz)(acac)(2)(NO(3))] (3, 4) and [La(pydppz)(anacac)(2)(NO(3))] (5), where Ln is La(III) (in 1, 3, 5) and Gd(III) (in 2, 4), pyphen is 6-(2-pyridyl)-1,10-phenanthroline, pydppz is 6-(2-pyridyl)-dipyrido[3,2-a:2',3'-c]phenazine, anacac is anthracenylacetylacetonate and acac is acetylacetonate, were prepared, characterized and their DNA photocleavage activity and photocytotoxicity studied. The crystal structure of complex 2 displays a GdO(6)N(3) coordination. The pydppz complexes 3-5 show an electronic spectral band at ~390 nm in DMF. The La(III) complexes are diamagnetic, while the Gd(III) complexes are paramagnetic with seven unpaired electrons. The molar conductivity data suggest 1 : 1 electrolytic nature of the complexes in aqueous DMF. They are avid binders to calf thymus DNA giving K(b) in the range of 5.4 × 10(4)-1.2 × 10(6) M(-1). Complexes 3-5 efficiently cleave supercoiled DNA to its nicked circular form in UV-A light of 365 nm via formation of singlet oxygen ((1)O(2)) and hydroxyl radical (HO˙) species. Complexes 3-5 also exhibit significant photocytotoxic effect in HeLa cancer cells giving respective IC(50) value of 0.16(±0.01), 0.15(±0.01) and 0.26±(0.02) μM in UV-A light of 365 nm, while they are less toxic in dark with an IC(50) value of >3 μM. The presence of an additional pyridyl group makes the pydppz complexes more photocytotoxic than their dppz analogues. FACS analysis of the HeLa cells treated with complex 4 shows apoptosis as the major pathway of cell death. Nuclear localization of complex 5 having an anthracenyl moiety as a fluorophore is evidenced from the confocal microscopic studies.

  1. Mercury coordination polymers with flexible ethane-1,2-diyl-bis-(pyridyl-3-carboxylate): Synthesis, structures, thermal and luminescent properties

    SciTech Connect

    Vallejos, Javier; Brito, Iván; Cárdenas, Alejandro; Llanos, Jaime; Bolte, Michael; López-Rodríguez, Matías

    2015-03-15

    The reaction of the flexible ligand, ethane-1,2-diyl-bis-(pyridyl-3-carboxylate), (L) with HgI{sub 2} and HgBr{sub 2} salts under the same experimental conditions leads to the formation of two coordination polymers with different motifs: ([Hg(L)(Br{sub 2})]){sub n}(1) and ([Hg(L)(I{sub 2})]){sub n}(2). In both compounds, the ligand, (L) acts in a μ2-N:N′-bidentate fashion to link HgBr{sub 2} and HgI{sub 2} units to form a linear and helical chain motif, along [1 0 0] for (1) and [0 0 1] for (2). The ethylene moiety of (L) has gauche and trans conformation in compounds (1) and (2), respectively. The flexible conformation of L produces differences in the optical and crystal properties of the two compounds. - Graphical abstract: This work demonstrates how the HgX{sub 2} units are coordinates by bi-dentate ligand forming polymeric coordination complexes by self-assembly of both chemical units.- Highlights: • News 1-D d{sup 10} transition metal coordination polymers. • The photoluminescent properties have been measured. • The thermal properties have been measured.

  2. Syntheses, structure and properties of three-dimensional pillared-layer Ag(I)-Ln(III) heterometallic coordination polymers based on mixed isonicotinate and hemimellitate ligands

    SciTech Connect

    Li, Xinfa; Cao, Rong

    2012-12-15

    Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers (HCPs), formulated as [Ln{sub 2}Ag(hma){sub 2}(ina)(H{sub 2}O){sub 2}]{sub n} nH{sub 2}O [Ln=La(1), Pr(2), Nd(3); Hina=isonicotinic acid, H{sub 3}hma=hemimellitic acid], have been synthesized under hydrothermal conditions. Single-crystal and powder X-ray diffractions confirm that they are isostructural, which features a three-dimensional (3D) pillared-layer heterometallic structure built upon the strictly alternate arrangement of lanthanide-organic layers and [Ag(ina)] pillars. The layers and pillars are connected to each other by Ln-O and Ag-O coordination bonds. The photoluminescent property of the Nd derivative (3) has also been investigated. - Graphical abstract: Three pillared-layer 4d-4f Ag(I)-Ln(III) heterometallic coordination polymers have been synthesized and structurally characterized. Highlights: Black-Right-Pointing-Pointer Three 3D pillared-layer 4d-4f HCPs were synthesized by hydrothermal reactions. Black-Right-Pointing-Pointer The synergistic coordination strategy was employed. Black-Right-Pointing-Pointer It opens new perspective for the construction of structurally diversified 4d-4f HCPs.

  3. C-H⋯Cl relevant discrepancy on structure, magnetic and electronic conductivity of two mixed-valence Cu ICu II coordination polymers

    NASA Astrophysics Data System (ADS)

    Shi, Ling; Yang, Ping; Huang, Guang; Li, Qian; Wang, Ning; Wu, Jian-Zhong; Yu, Ying

    2011-07-01

    Two mixed-valence Cu ICu II coordination polymers [Cu ICu II(qdiol)ClL] n (qdiol 2-=2,3-dioxyquinoxalinate, L=2,2'-bipyridine, 1; L=1,10-phenanthroline, 2) were obtained in basic ethanolic solution of CuCl 2, 1,4-dihydro-2,3-quinoxalinedione and L under the solvothermal condition. 1 and 2 are similar in composition, but differ remarkably in structure. The coordination modes of Cu II, qdiol 2- and L are identical in both complexes. But the Cu I ions are two- and three-coordinated, and the Cl - ions are terminal and bridging, in 1 and 2, respectively, which are relevant to the significantly different C-H⋯Cl hydrogen bonding pattern of bpy and phen. The temperature variable magnetic susceptibilities show that 1 is paramagnetic and 2 is weakly antiferromagnetic. The complex impedance spectroscopic studies indicate that both 1 and 2 are semiconductors and 2 is more conducting.

  4. Two-dimensional Zn(II) and one-dimensional Co(II) coordination polymers based on benzene-1,4-dicarboxylate and pyridine ligands.

    PubMed

    Zhou, Li-Juan; Han, Chang-Bao; Wang, Yu-Ling

    2016-02-01

    Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene-1,4-dicarboxylic acid (H2BDC) and pyridine (py) with Zn(II) or Co(II) yielded two new coordination polymers, namely, poly[(μ4-benzene-1,4-dicarboxylato-κ(4)O:O':O'':O''')(pyridine-κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena-poly[aqua(μ3-benzene-1,4-dicarboxylato-κ(3)O:O':O'')bis(pyridine-κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the Zn(II) cation is five-coordinated by four carboxylate O atoms from four BDC(2-) ligands and one pyridine N atom in a distorted square-pyramidal coordination geometry. Four carboxylate groups bridge two Zn(II) ions to form centrosymmetric paddle-wheel-like Zn2(μ2-COO)4 units, which are linked by the benzene rings of the BDC(2-) ligands to generate a two-dimensional layered structure. The two-dimensional layer is extended into a three-dimensional supramolecular structure with the help of π-π stacking interactions between the aromatic rings. Compound (II) has a one-dimensional double-chain structure based on Co2(μ2-COO)2 units. The Co(II) cations are bridged by BDC(2-) ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC(2-) ligands, one water O atom and two pyridine N atoms. Interchain O-H...O hydrogen-bonding interactions link these chains to form a three-dimensional supramolecular architecture. PMID:26846498

  5. Improved synthesis of 4,4'-bipyridine-2-carboxylic acid and its use in the construction of novel metal and mixed-metal coordination polymers

    NASA Astrophysics Data System (ADS)

    Ellsworth, Joseph M.; Smith, Mark D.; zur Loye, Hans-Conrad

    2008-12-01

    An improved synthesis of 4,4'-bipyridine-2-carboxylic acid (ppcaH) has significantly increased the yield and thus enabled the preparation of four new coordination compounds that contain copper, cobalt, and vanadium or molybdenum oxide. Each structure was synthesized solvothermally and characterized by both powder and single-crystal X-ray diffraction. Cu(ppca) 2 ( 1) is a discrete molecular complex that crystallizes in the P2 1/ c space group, a = 5.0749(4) Å, b = 25.442(2) Å, c = 7.2536(6) Å. Co(ppca)(SCN)(H 2O) ( 2) is a H-bonded 2D coordination polymer that crystallizes in the P2 1/ c space group, a = 11.0716(4) Å, b = 11.2327(4) Å, c = 10.2073(4) Å. [Cu(ppca)(Hppca)] 2[H 2Mo 4O 14] ( 3) and Co(ppca) 2(V 2O 6)(H 2O) ( 4) are mixed-metal coordination polymers that crystallize in the P1¯ and Pbca space groups, respectively. Complex ( 3) is a 2D framework that contains an H 2Mo 4O 142- anion, a = 8.4019(6) Å, b = 8.6990(6) Å, c = 16.8513(12) Å, while ( 4) is a highly ordered H-bonded 3D mixed-metal coordination polymer whose vanadate cluster species was generated in situ using a tetramethyl ammonium hydroxide and acetic acid buffer solution, a = 18.0118(8) Å, b = 11.2664(5) Å, c = 25.3385(11) Å.

  6. Synthesis, crystal structures and luminescent properties of two 4d-4f Ln-Ag heterometallic coordination polymers based on anion template

    SciTech Connect

    Fan, Le-Qing; Chen, Yuan; Wu, Ji-Huai; Huang, Yun-Fang

    2011-04-15

    Two new 4d-4f Ln-Ag heterometallic coordination polymers, {l_brace}[Ln{sub 3}Ag{sub 5}(IN){sub 10}(H{sub 2}O){sub 7}].4(ClO{sub 4}).4(H{sub 2}O){r_brace}{sub n} (Ln=Eu (1) and Sm (2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions by reactions of Ln{sub 2}O{sub 3}, AgNO{sub 3}, HIN and HClO{sub 4}, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. It is proved that HClO{sub 4} not only adjusts the pH value of the reaction mixture, but also acts as anion template. The structure determination reveals that 1 and 2 are isostructural and feature a novel two-dimensional (2D) layered hetrometallic structure constructed from one-dimensional Ln-carboxylate chains and pillared Ag(IN){sub 2} units. The 2D layers are further interlinked through Ag...Ag and Ag...O(ClO{sub 4}{sup -}) multiple weak interactions, which form a rare Ag-ClO{sub 4} ribbon in lanthanide-transition metal coordination polymers, to give rise to a three-dimensional supramolecular architecture. Moreover, the luminescent properties of these two compounds have also been investigated at room temperature. -- Graphical abstract: Two new anion-templated 2D 4d-4f Ln-Ag heterometallic coordination polymers based on novel lanthanide-carboxylate chains and pillared Ag(IN){sub 2} units, {l_brace}[Ln{sub 3}Ag{sub 5}(IN){sub 10}(H{sub 2}O){sub 7}].4(ClO{sub 4}).4(H{sub 2}O){r_brace}{sub n} (Ln=Eu (1) and Sm (2), HIN=isonicotinic acid), have been hydrothermally synthesized and structurally characterized. 1 and 2 exhibit good luminescent properties. Display Omitted Research highlights: > Two 2D Eu (Sm)-Ag coordination polymers templated by perchlorate anion have been synthesized. > Polymers consist of novel 1D lanthanide-carboxylate chains. > In both structures, there are rare Ag...Ag and Ag...O(ClO{sub 4}{sup -}) multiple weak interactions. > Both compounds exhibit good luminescent properties.

  7. A general method for preparing lanthanide oxide nanoparticles via thermal decomposition of lanthanide(III) complexes with 1-hydroxy-2-naphthoic acid and hydrazine ligands

    NASA Astrophysics Data System (ADS)

    Parimalagandhi, Karuppannan; Premkumar, Thathan; Vairam, Sundararajan

    2016-09-01

    Six new lanthanide(III) complexes (i.e., [Ln(L)2(NA)1.5]·3H2O, where Ln=La(III), Pr(III), Nd(III), Sm(III), Gd(III), and Ce(III) and L and NA indicate N2H4 and C10H6(1-O)(2-COO), respectively) with 1-hydroxy-2-naphthoic acid [C10H6(1-O)(2-COOH)] and hydrazine (N2H4) as co-ligands were characterized by elemental, FTIR, UV-visible, and XRD techniques. In the FT-IR spectra, the N-N stretching frequency in the range of 981-949 cm-1 demonstrates evidence of the presence of coordinated N2H4, indicating the bidentate bridging nature of hydrazine in the complexes. These complexes show symmetric and asymmetric COO- stretching from 1444 to 1441 cm-1 and 1582 to 1557 cm-1, respectively, indicating bidentate coordination. TG-DTA studies revealed that the compounds underwent endothermic dehydration from 98 to 110 °C. This was followed by the exothermic decomposition of oxalate intermediates to yield the respective metal oxides as the end products. From SEM images, the average size of the metal oxide particles prepared by thermal decomposition of the complexes was determined to be 39-42 nm. The powder X-ray and SEM coupled with energy dispersive X-ray (EDX) studies revealed the presence of the respective nano-sized metal oxides. The kinetic parameters of the decomposition of the complexes were calculated using the Coats-Redfern equation.

  8. One-dimensional coordination polymers: Cu(II) and Zn(II) complexes of N-(2-pyridylmethyl)-glycine and N-(2-pyridylmethyl)- L-alanine

    NASA Astrophysics Data System (ADS)

    Wang, Xiaobai; Ranford, John D.; Vittal, Jagadese J.

    2006-08-01

    The crystal structures of three Cu(II) and one Zn(II) complexes of N-(2-pyridylmethyl)- L-glycine (Hpgly) and N-(2-pyridylmethyl)- L-alanine (Hpala) have been described. They are [Cu(pgly)Cl] · H 2O ( 1), [Cu(pala)Cl] · H 2O ( 2), [Cu(pala)(CH 3COO)] · 0.75H 2O ( 3), and [Zn(pgly)(NO 3)] ( 4). All these compounds have 1D polymeric structures in the solid state. In 1 and 2, the chloride ions bridge [Cu(pgly)] and [Cu(pala)] fragments, respectively, to generate 1D polymers while the bridging acetate ligands are responsible for the formation of ΛΔΛΔ type spiral polymers in 3. The nitrate ion in 4 is only acting as a terminal ligand while the carboxylate oxygen atom of the pala ligand bridges the Zn(II) centers to form the zigzag coordination polymeric chain. The 1D coordination polymers in 1 and 2 have very similar arrangements although crystallized in different space groups, and host 1D water chains in their crystal lattices.

  9. Solvent induced synthesis, structure and properties of coordination polymers based on 5-hydroxyisophthalic acid as linker and 1,10-phenanthroline as auxiliary ligand

    NASA Astrophysics Data System (ADS)

    Kariem, Mukaddus; Yawer, Mohd; Sheikh, Haq Nawaz

    2015-11-01

    Three new coordination polymers [Mn(hip)(phen) (H2O)]n (1), [Co(hip)(phen) (H2O)]n (2), and [Cd(hip) (phen) (H2O)]n (3) (H2hip=5-hydroxyisophthalic acid; phen=1,10-phenanthroline) have been synthesized by solvo-hydrothermal method using diethyl formamide-water (DEF-H2O) as solvent system. Single-crystal X-ray diffraction analysis reveals that all three coordination polymers 1, 2 and 3 crystallize in monoclinic space group P2/n. Metal ions are inter-connected by hydroxyisophthalate anions forming zig-zag 1D chain. 1D chains are further inter-connected by hydrogen bonding and π-π stacking interactions leading to 3D supramolecular architecture. Hydrogen-bonding and π-π stacking provide thermal stability to polymers. Compounds 1 and 2 are paramagnetic at room temperature and variable temperature magnetic moment measurements revealed weak ferromagnetic interactions between metal ions at low temperature. Compound 3 exhibits excellent photoluminescence with large Stokes shift.

  10. Synthesis, structures and properties of a family of four two-dimensional coordination polymers constructed from 5-hydroxyisophthalate

    SciTech Connect

    Zhang, Kou-Lin; Zhang, Jing-Bo; Jing, Chu-Yue; Zhang, Lei; Walton, Richard I.; Zhu, Peizhi; Ng, Seik Weng

    2014-03-15

    Four 2D coordination polymers (CPs) with different structures containing the multifunctional ligand 5-hydroxyisophthalate (5-OH-BDC{sup 2−}), [Zn(5-OH-BDC)(btb)]·2H{sub 2}O (1), [Cd(5-OH-BDC)(btp)(H{sub 2}O)]·3H{sub 2}O (2), [Cd(5-OH-BDC)(bth){sub 2}(H{sub 2}O)]·H{sub 2}O (3) and [Pb(5-OH-BDC)]·H{sub 2}O (4) [btp=1, 3-bis(1,2,4-triazol-1-yl)propane, btb=1,4-bis(1,2,4-triazol-1-yl)butane, bth=1, 6-bis(1,2,4-triazol-1-yl)hexane] were obtained. 1–3 were synthesised hydrothermally, while 4 was obtained under ambient condition. The adjacent (2D→2D) polycatenated 2D layers of 1 polythread in a parallel manner to form an unusual 2D→3D polythreaded framework. 2 contains an undulated 2D (4, 4) network and further extends into an “embracing” double-layer structure through the C–H···π and π···π stacking interactions. 3 exhibits a non-interpenetrating 2D (4, 4)-network. 4 exhibits a 2D double-layered binodal (4, 4)-net containing oblong nanochannels with symbol (4{sup 3}6{sup 3}){sub 2}. Reversible dehydration–rehydration is observed in 1, 2 and 4, which fall within the category of “recoverable collapsing” and “guest-induced re-formation” frameworks, while 3 exhibits irreversible dehydration–rehydration behaviour. The solid state fluorescent properties of 1–4 have been investigated. -- Graphical abstract: Among four 2D CPs reported, 1 is an unusual 2D→3D polythreaded framework. 4 exhibits 2D double-layered binodal (4, 4)-net containing nanochannels. Reversible dehydration–rehydration is observed in 1, 2 and 4. Highlights: • Four 2D CPs based on 5-hydroxyisophthalate with d{sup 10} and Pb(II) ions were reported. • 1 is an unusual 2D→3D polythreaded framework. • 4 shows a binodal (4, 4)-connected 2D double-layer network with nanochannels. • The materials 1, 2 and 4 show reversible dehydration–rehydration behaviours. • Solid state fluorescent properties were investigated.

  11. Transition metal coordination polymers based on tetrabromoterephthalic and bis(imidazole) ligands: Syntheses, structures, topological analysis and photoluminescence properties

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaowei; Xing, Peiqi; Geng, Xiujuan; Sun, Daofeng; Xiao, Zhenyu; Wang, Lei

    2015-09-01

    Eight new coordination polymers (CPs), namely, [Zn(1,2-mbix)(tbtpa)]n (1), [Co(1,2-mbix)(tbtpa)]n (2), [CdCl(1,2-mbix)(tbtpa)0.5]n (3), {[Cd(1,2-bix)(tbtpa)]·H2O}n (4), {[Cd0.5(1,2-bix)(tbtpa)0.5]·H2O}n (5), {[Co0.5(1,2-bix)(tbtpa)0.5]·2H2O}n (6), {[Co(1,2-bix)(tbtpa)]·H2O}n (7) and {[Co(1,2-bix)(tbtpa)]·Diox·2H2O}n (8), were synthesized under solvothermal conditions based on mix-ligand strategy (H2tbtpa=tetrabromoterephthalic acid and 1,2-mbix=1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,2-bix=1,2-bis(imidazol-1-ylmethyl)benzene). All of the CPs have been structurally characterized by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). X-ray diffraction analyses show that 1 and 2 are isotypics which have 2D highly undulated networks with (4,4)-sql topology with the existence of C-H ⋯Br interactions; for 3, it has a 2D planar network with (4,4)-sql topology with the occurrence of C-H ⋯Cl interactions other than C-H ⋯Br interactions; 4 shows a 3D 2-fold interpenetrated nets with rare 65·8-mok topology which has a self-catention property. As the same case as 1 and 2, 5 and 6 are also isostructural with planar layers with 44-sql topology which further assembled into 3D supramolecular structure through the interdigitated stacking fashion and the C-Br ⋯Cph interactions. As for 7, it has a 2D slightly undulated networks with (4,4)-sql topology which has one dimension channel. While 8 has a 2-fold interpenetrated networks with (3,4)-connect jeb topology with point symbol {63}{65·8}. And their structures can be tuned by conformations of bis(imidazol) ligands and solvent mixture. Besides, the TGA properties for all compounds and the luminescent properties for 1, 3, 4, 5 are discussed in detail.

  12. A series of divalent metal coordination polymers based on isomeric tetracarboxylic acids: synthesis, structures and magnetic properties.

    PubMed

    Han, Min-Le; Duan, Ya-Ping; Li, Dong-Sheng; Xu, Guo-Wang; Wu, Ya-Pan; Zhao, Jun

    2014-12-14

    Five new coordination polymers, namely, [Mn(2,2′-bipy)(H2O)2(H2L1)]n (1), {[Co(btb)(H2O)2(H2L1)]·0.5H2O}n (2), [Co(bib)(H2O)2(H2L1)]n (3), [Ni2(bpm)(H2O)3(L2)]n (4), and {[Co2(H2O)3(OH)(HL2)]·H2O}n (5), (H4L1 = 1,1′:2′,1′′-terphenyl-4,4′,4′′,5′-tetracarboxylic acid, H4L2 = 1,1′:2′,1′′-terphenyl-3,3′′,4′,5′-tetracarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bib = 1,4-bis(imidazol-1-yl)butane, bpm = bis(4-pyridyl)amine), have been obtained under hydrothermal conditions. Complex 1 exhibits a 3D supramolecular framework based on 1D chains. Both complexes 2 and 3 are 3D supramolecular frameworks constructed from 1D zig-zag chains. Complex 4 features a 3D tetra-nodal (3,4,4,5)-connected architecture containing 1D μ-COO bridged chains with (5(2)·6(2)·7.9)(5(2)·6(4)·7(3)·8)2(5(2)·6)2(6(3)·7(2)·9) topology. Complex 5 shows a 3D penta-nodal (3,4,4,6,6)-connected net containing 1D μ-OH/μ-COO bridged chains and mononuclear Co(II) nodes with a (4(2)·6(3)·8)(4(3))2(4(4)·6(2))2(4(4)·6(6)·8(5))2(4(4)·6(7)·8(4)) topology. Variable-temperature magnetic susceptibility measurements reveal that complexes 2 and 3 show antiferromagnetic interactions between the adjacent Co(II) ions, whereas 4 is a ferromagnetic system. PMID:25347690

  13. A two-dimensional zinc(II) coordination polymer based on mixed dimethyl succinate and bipyridine ligands: synthesis, structure, thermostability and luminescence properties.

    PubMed

    Liu, Yang; Feng, Yong Lan; Fu, Wei Wei

    2016-04-01

    From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self-assembly process. Multicarboxylate ligands are of particular interest due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of dicarboxylate-based coordination polymers of transition metals has been developed through the grafting of N-containing organic linkers into carboxylate-bridged transition metal networks. A new luminescent two-dimensional zinc(II) coordination polymer containing bridging 2,2-dimethylsuccinate and 4,4'-bipyridine ligands, namely poly[[aqua(μ2-4,4'-bipyridine-κ(2)N:N')bis(μ3-2,2-dimethylbutanedioato)-κ(4)O(1),O(1'):O(4):O(4');κ(5)O(1):O(1),O(4):O(4),O(4')-dizinc(II)] dihydrate], {[Zn2(C6H8O4)2(C10H8N2)(H2O)]·2H2O}n, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2-dimethylsuccinate ligands link linear tetranuclear Zn(II) subunits into one-dimensional chains along the c axis. 4,4'-Bipyridine acts as a tethering ligand expanding these one-dimensional chains into a two-dimensional layered structure. Hydrogen-bonding interactions between the water molecules (both coordinated and free) and carboxylate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic-organic photoactive materials.

  14. Syntheses, structures and properties of two new coordination polymers based on D-camphoric acid and 2-phenyl-4,6-diamino-1,3,5-triazine

    SciTech Connect

    Lun, Huijie; Yang, Jinghe; Jin, Linyu; Cui, Sasa; Bai, Yanlong; Zhang, Xudong; Li, Yamin

    2015-05-15

    By hydrothermal method, two new coordination polymers [Co(ca)(phdat)]{sub n} (1), [Ni(ca)(phdat).0.125H{sub 2}O]{sub n} (2) (H{sub 2}ca=D-camphoric acid, phdat=2-phenyl-4,6-diamino-1,3,5-triazine) have been achieved and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isostructural, both of which exhibit two-dimensional layered network built up from paddle-wheel Co{sub 2}(CO{sub 2}){sub 4}/Ni{sub 2}(CO{sub 2}){sub 4} SBUs by ca{sup 2−} ligand. In the existence of π…π stacking interactions between triazine rings and phenyl rings, the 3D networks are constructed with the hanging phdat filled between the neighboring layers. Furthermore, compounds 1–2 exhibit antiferromagnetic behavior and compound 2 displays a good activity for methanol oxidation. - Graphical abstract: Two new coordination compounds 1–2 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses, magnetic and electrochemical measurement. - Highlights: • This paper reports two new coordination polymers based on D-camphoric acid. • Both the compounds feather two-dimensional layered networks built up from paddle-wheel SBUs. • The magnetism and electrochemical property are investigated.

  15. A novel three-dimensional AgI coordination polymer based on mixed naphthalene-1,5-disulfonate and aminoacetate ligands.

    PubMed

    Wu, Hua; Lü, Xiao-Li; Lü, Bo; Dong, Chang-Xun; Wu, Mei-Sheng

    2013-08-01

    The three-dimensional coordination polymer poly[[bis(μ₃-2-aminoacetato)di-μ-aqua-μ₃-(naphthalene-1,5-disulfonato)-hexasilver(I)] dihydrate], {[Ag₆(C₁₀H₆O₆S₂)(C₂H₄NO₂)₄(H₂O)₂]·2H₂O}n, based on mixed naphthalene-1,5-disulfonate (L1) and 2-aminoacetate (L2) ligands, contains two Ag(I) centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five-coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one AgI cation in a distorted trigonal-bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two AgI cations in a slightly octahedral coordination geometry. Ag3 is four-coordinated by two O atoms from two L2 anions and two AgI cations in a slightly distorted square geometry, while Ag4 is also four-coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one AgI cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one-dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two-dimensional layer, and the layers are further bridged by L1 anions to generate a novel three-dimensional framework. Moreover, hydrogen-bonding interactions consolidate the network.

  16. Two 2D Cd(II) coordination polymers based on asymmetrical Schiff-base ligand: Synthesis, crystal structures and luminescent properties

    NASA Astrophysics Data System (ADS)

    Dang, Dong-Bin; Li, Meng-Meng; Bai, Yan; Zhou, Rui-Min

    2013-02-01

    Two new two-dimensional coordination polymers [Cd3L2(SCN)6]n (1) and [CdLI2]n (2) have been synthesized and characterized by IR spectroscopy, elemental analysis, TG technique, XRPD and complete single crystal structure analysis, where L is 4-(pyridine-2-yl)methyleneamino-1,2,4-trizaole. Asymmetrical Schiff-base ligand L with five- and six-membered N-containing heterocyclic rings acts as a tridentate bridging ligand to bind two Cd(II) centers through one terminal Ntriazolyl and one pyridylimine chelate unit in 1 and 2. For polymer 1, tridentate bridging ligands link Cd-(1,3-μ-SCN-) 1D inorganic chains to form a 2D layer network. The existence of Csbnd H⋯π and πsbnd π stacking interactions between 2D hybrid layers further gives rise to a 3D supramolecular network. In comparison with 1, polymer 2 shows a 2D layer network containing hexanuclear macrometallacyclic units. The 2D layers are staggered together through the combination of Csbnd H⋯π and πsbnd π stacking interactions and forming a 3D supramolecular structure. The luminescent properties of the polymers 1 and 2 were investigated in the solid state at room temperature.

  17. Synthesis, structural characterization and microbial activity of 2D Ag(I)-5-aminoisophthalate coordination polymer with a new coordination mode

    NASA Astrophysics Data System (ADS)

    Günay, Handan; Çolak, Alper Tolga; Yeşilel, Okan Zafer; Tunç, Tuncay; Çolak, Ferdağ

    2015-11-01

    In this study, a novel polynuclear Ag(I)-5-aminoisophthalate complex [Ag(μ4-Haip)]n (1) (H2aip = 5-aminoisophthalic acid) has been synthesized. The molecular structure of this complex has been determined by the single crystal X-ray diffraction. The two-dimensional polynuclear complex is crystallized in the triclinic crystal system with space group P-1. The Ag(I) ion is four-coordinated by three carboxylate oxygen atoms of three different Haip ligands and one nitrogen atom in a distorted tetrahedral geometry. Furthermore, a novel coordination mode has shown by H2aip. This complex exhibits photoluminescence in the solid state at room temperature. Antimicrobial activity of complex was evaluated by the agar diffusion method. The complex showed antimicrobial activity against tested microorganism strains (Gram positive, gram negative bacteria, clinic isolate yeast and mold). Moreover this complex showed particularly high antifungal activity against yeast and mold.

  18. In situ ligand generation for novel Mn(II) and Ni(II) coordination polymers with disulfide ligand: Solvothermal syntheses, structures and magnetic properties

    SciTech Connect

    Han, Yinfeng Wang, Chang'an; Zheng, Zebao; Sun, Jiafeng; Nie, Kun; Zuo, Jian; Zhang, Jianping

    2015-07-15

    Two coordination polymers, ([Mn{sub 2}(L1){sub 2}(μ{sub 2}-H{sub 2}O)(H{sub 2}O){sub 4}]·5H{sub 2}O){sub n}1 and ([Ni(L1)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n}2 (H{sub 2}L1=2,2′-dithiobisnicotinic acid), were prepared by the solvothermal reactions of the Mn(II) or Ni(II) ions with 2-mercaptonanicotinic acid. In 1, the [Mn{sub 2}(COO){sub 4}] units are connected by the 2,2′-dithiobisnicotinic dianion to form a two-dimensional (4,4)-connected network. In 2, the adjacent Ni(II) ions are connected by the carboxyl groups of the 2,2′-dithiobisnicotinic dianion to form an one-dimensional inorganic rod-shaped chain [Ni(COO){sub 2}]{sub n}, which are further interconnected by the 2,2′-dithiobisnicotinic ligand, giving rise to a two-dimensional framework. Variable-temperature magnetic susceptibilities of 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent metal ions. - Graphical abstract: Two 2D coordination polymers were synthesized by transition-metal/in-situ oxidation of 2-mercaptonicotinic acid. The compounds pack into 2D frameworks by the carboxyl groups of 2,2′-dithiobisnicotinic dianion and exhibit overall weak antiferromagnetic coupling. - Highlights: • Two 2D coordination polymers containing 2,2′-dithiobisnicotinic dianion. • In situ oxidation and dehydro coupling reaction of 2-mercaptonbenzoic acid. • Two compounds display weak antiferromagnetic exchanges.

  19. Metal-controlled assembly tuning the topology and dimensionality of coordination polymers of Ag(I), Cd(II) and Zn(II) with the flexible 2-(1 H-imidazole-1-yl)acetic acid (Hima)

    NASA Astrophysics Data System (ADS)

    Wang, Yong-Tao; Tang, Gui-Mei; Wu, Yue; Qin, Xu-Yan; Qin, Da-Wei

    2007-04-01

    Three new, inorganic-organic coordination polymers based on a versatile linking unit 2-(1 H-imidazole-1-yl)acetate (ima) and Ag I, Cd II and Zn II ions, exhibiting one to three dimensionalities and different topology structures, have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of AgNO 3 with Hima afforded a neutral one-dimensional (1-D) chains [Ag(ima)] n ( 1) which exhibits a pseudo two-dimensional (2-D) layered architecture through π-π stacking interaction between imidazole rings and intermolecular Ag⋯Ag interactions. Reaction of CdCl 2 with Hima yielded neutral 2-D coordination polymers [Cd(ima) 2] n ( 2) possessing (6, 3) topology structures, which further stack into 3-D supramolecular networks through C-H⋯O weak interactions. While Zn(NO 3) 2 was used, a non-centric 3-D coordination polymer [Zn(ima) 2] n ( 3) featuring a 3-fold interpenetrating diamondoid net was isolated. Among these polymers, the building block ima anion exhibits different coordination modes. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal ions, play a critical role in construction of these novel coordination polymers. The spectral, thermal and SHG (second-harmonic generation) properties of these new materials have also been investigated.

  20. Synthesis and explosive properties of copper(II) chlorate(VII) coordination polymer with 4-amino-1,2,4-triazole bridging ligand.

    PubMed

    Cudziło, Stanisław; Nita, Marcin

    2010-05-15

    Copper(II) chlorate(VII) coordination polymer with 4-amino-1,2,4-triazole as bridging ligand was prepared and characterized by elemental analysis, IR spectra and TG/DTA analyses. Sensitivity and detonator tests were also preformed. The compound has a 1D chain structure in which Cu(II) ions are linked by triple triazole N1,N2 bridges. It is a detonat with performance close to that of lead azide, but at the same time it shows moderate sensitivity to thermal (explosively decomposes above 250 degrees C) and mechanical stimuli (sensitivity to friction 10N).

  1. Spontaneous resolution to absolute chiral induction: pseudo-Kagomé type homochiral Zn(II)/Co(II) coordination polymers with achiral precursors.

    PubMed

    Bisht, Kamal Kumar; Suresh, Eringathodi

    2013-10-23

    It is observed that conglomerate crystallization of achiral precursors yielding racemate metal organic frameworks/coordination polymers (MOFs/CPs) can be driven to absolute homochiral crystallization of the desired enantiomorph by utilizing a suitable chiral induction agent. In a series of crystallization experiments isostructural Zn and Co homochiral CPs (1P, 1M and 2P, 2M) are prepared using the achiral precursors. In the presence of enantiopure camphoric acid, the crystallization process prefers absolute chiral induction over conglomerate formation which is established by single crystal X-ray diffraction and CD spectroscopy.

  2. Two-dimensional coordination polymers constructed using, simultaneously, linear and angular spacers and cobalt(II) nodes. New examples of networks of single-ion magnets.

    PubMed

    Ion, Adrian E; Nica, Simona; Madalan, Augustin M; Shova, Sergiu; Vallejo, Julia; Julve, Miguel; Lloret, Francesc; Andruh, Marius

    2015-01-01

    Two novel bidimensional coordination polymers, [Co(azbbpy)(4,4'-bipy)0.5(DMF)(NCS)2]·MeOH (1) and [Co(azbbpy)(bpe)0.5(DMF)(NCS)2]·0.25H2O (2), resulted from the assembling of cobalt(II) ions by 1,3-bis(4-pyridyl)azulene, using either 4,4'-bipyridyl or 1,2-bis(4-pyridyl)ethylene as neutral spacers. The cobalt(II) nodes in 1 and 2 act as single-ion magnets (SIMs).

  3. Single-ion-magnet behavior in a two-dimensional coordination polymer constructed from Co(II) nodes and a pyridylhydrazone derivative.

    PubMed

    Liu, Xiangyu; Sun, Lin; Zhou, Huiliang; Cen, Peipei; Jin, Xiaoyong; Xie, Gang; Chen, Sanping; Hu, Qilin

    2015-09-21

    A novel two-dimensional (2D) coordination polymer, [Co(ppad)2]n (1), resulted from the assembly of Co(II) ions based on a versatile ligand termed N(3)-(3-pyridoyl)-3-pyridinecarboxamidrazone. Alternating/direct-current magnetic studies of compound 1 indicate that the spatially separated high-spin Co(II) ions act as single-ion magnets (SIMs). The present work represents the first case of a 2D Co(II)-based SIM composed of a monocomponent organic spacer.

  4. Formation of Foam-like Microstructural Carbon Material by Carbonization of Porous Coordination Polymers through a Ligand-Assisted Foaming Process.

    PubMed

    Kongpatpanich, Kanokwan; Horike, Satoshi; Fujiwara, Yu-Ichi; Ogiwara, Naoki; Nishihara, Hirotomo; Kitagawa, Susumu

    2015-09-14

    Porous carbon material with a foam-like microstructure has been synthesized by direct carbonization of porous coordination polymer (PCP). In situ generation of foaming agents by chemical reactions of ligands in PCP during carbonization provides a simple way to create lightweight carbon material with a foam-like microstructure. Among several substituents investigated, the nitro group has been shown to be the key to obtain the unique foam-like microstructure, which is due to the fast kinetics of gas evolution during carbonization. Foam-like microstructural carbon materials showed higher pore volume and specific capacitance compared to a microporous carbon.

  5. A novel one-dimensional manganese(II) coordination polymer containing both dicyanamide and pyrazinamide ligands: Synthesis, spectroscopic investigations, X-ray studies and evaluation of biological activities

    NASA Astrophysics Data System (ADS)

    Tabrizi, Leila; Chiniforoshan, Hossein; McArdle, Patrick

    2015-03-01

    A novel 1D coordination polymer {[Mn(μ1,5-dca)2(PZA)2](PZA)2}n, 1, has been synthesized and characterized by single crystal X-ray crystallography. The coordination mode of dicyanamide (dca) and pyrazinamide (PZA) ligands was inferred by IR spectroscopy. The compound 1 was evaluated for in vitro antimycobacterial and antitumor activities. It demonstrated better in vitro activity against Mycobacterium tuberculosis than pyrazinamide and its MIC value was determined. Complex 1 was also screened for its in vitro antitumor activity towards LM3 and LP07 murine cancer cell lines. In addition, the antibacterial activity of complex 1 has been tested against Gram(+) and Gram(-) bacteria and it has shown promising broad range anti-bacterial activity.

  6. Synthesis, vibrational spectroscopy and crystal structure of zinc and sodium tricarboxylate coordination polymers with the flexible ligand tricarballylate anion (TCA 3-)

    NASA Astrophysics Data System (ADS)

    Williams, Patricia A. M.; Naso, Luciana G.; Echeverría, Gustavo A.; Ferrer, Evelina G.

    2010-08-01

    A new 3D coordination polymer of general formula [NaZn(C 6H 5O 6)(H 2O) 3] n has been hydrothermally synthesized and characterized by vibrational spectroscopy (Raman and Infrared), X-ray diffraction and thermal analysis. The compound crystallizes in the centrosymmetric monoclinic group C2/ c with a = 10.885(2), b = 13.219(3), c = 15.299(5) Å, β = 102.23(2)°, V = 2151(1) (Å 3), Z = 8. The crystal structure consists in an open framework where the arrangement of tetrahedral zinc and octahedral sodium cations, coordinated by water and carboxylate oxygens atoms, are linked by tricarballylate anions developing channels parallel to the [0 1-1] crystallographic direction. Thermogravimetric analysis indicates that the complex is thermally stable up to 200 °C.

  7. Assembly of 4-, 6- and 8-connected Cd(II) pseudo-polymorphic coordination polymers: Synthesis, solvent-dependent structural variation and properties

    NASA Astrophysics Data System (ADS)

    Li, Zhao-Hao; Xue, Li-Ping; Miao, Shao-Bin; Zhao, Bang-Tun

    2016-08-01

    The reaction of Cd(NO3)2·4H2O, 2,5-thiophenedicarboxylic acid (H2tdc) and 1,2-bis(imidazol-1‧-yl)methane (bimm) by modulating solvent systems yielded three highly connected pseudo-polymorphic coordination polymers based on different dinuclear [Cd2(CO2)2] subunits bridged by carboxylate groups. Single crystal structural analyses reveal structural variation from 4-connected 2D sql layer, 6-connected 2-fold interpenetrated 3D pcu to 8-connected 3D bcu-type network in compounds 1-3. The structural dissimilarity in the structures dependent on the coordination environments of Cd(II) ions and linking modes of mixed ligand influenced by different solvent systems during the synthesis process. Moreover, thermogravimetric and photoluminescence behaviors of 1-3 were also investigated for the first time, and all the complexes emit blue luminescence in the solid state.

  8. First examples of ternary lanthanide 5-aminoisophthalate complexes: Hydrothermal syntheses and structures of lanthanide coordination polymers with 5-aminoisophthalate and oxalate

    NASA Astrophysics Data System (ADS)

    Liu, Chong-Bo; Wen, Hui-Liang; Tan, Sheng-Shui; Yi, Xiu-Guang

    2008-05-01

    Two new lanthanide coordination polymers with mixed-carboxylates, [Ln(OX)(HAPA)(H 2O)] n[Ln = Eu ( 1), Ho ( 2); H 2APA = 5-aminoisophthalic acid; OX = oxalate] were obtained by hydrothermal reactions, and characterized by single crystal X-ray diffraction, elemental analysis and IR spectra. Complexes 1 and 2 are both 3-D supramolecular structure, in which lanthanide ions are bridged by oxalate and 5-aminoisophthalate ligands forming 2-D metal-organic framework, and 2-D networks are further architectured to form 3-D supramolecular structures by hydrogen bonds. The two carboxylate groups of H 2APA ligand are all deprotonated and exhibit chelating and bridging bidentate coordination modes, respectively, and the amino group in HAPA presents - NH3+ in the titled complexes. The thermogravimetric analysis was carried out to examine the thermal stability of the titled complexes. And the photoluminescence property of 1 was investigated.

  9. Syntheses, crystal structures and luminescent properties of two new 1D d {sup 1} coordination polymers constructed from 2,2'-bibenzimidazole and 1,4-benzenedicarboxylate

    SciTech Connect

    Wen Lili; Li Yizhi; Dang Dongbin; Tian Zhengfang; Ni Zhaoping; Meng Qingjin . E-mail: mengqj@nju.edu.cn

    2005-11-15

    Two novel interesting d {sup 1} metal coordination polymers, [Zn(H{sub 2}bibzim)(BDC)] {sub n} (1) and [Cd(H{sub 2}bibzim)(BDC)] {sub n} (2) [H{sub 2}bibzim=2,2'-bibenzimidazole, BDC=1,4-benzenedicarboxylate] have been synthesized under solvothermal conditions and structurally characterized. Both 1 and 2 are constructed from infinite neutral zigzag-like one-dimensional (1D) chains. The {pi}-{pi} interactions and interchain hydrogen-bonding interactions further extend the 1D arrangement to generate a 3D supramolecular architecture for 1 and 2. Both complexes have high thermal stability and display strong blue fluorescent emissions in the solid state upon photo-excitation at 365 nm at room temperature. They are the first two examples that 2,2'-bibenzimidazole has been introduced into the d {sup 1} coordination polymeric framework.

  10. Dehydration induced 2D-to-3D crystal-to-crystal network re-assembly and ferromagnetism tuning within two chiral copper(II)-tartrate coordination polymers.

    PubMed

    Liu, Yen-Hsiang; Lee, Szu-Hsuan; Chiang, Jung-Chun; Chen, Po-Chen; Chien, Po-Hsiu; Yang, Chen-I

    2013-12-28

    The synthesis of two homochiral l-tartrate-copper(II) coordination polymers, [Cu2(C4H4O6)2(H2O)2·xH2O]n (1), and [Cu(C4H4O6)]n (2), under hydrothermal conditions, is reported. Compound 1 adopts a 2D layered network structure with a space group of P21, while compound 2 features a 3D network structure with a space group P21212. Interestingly, the 2D layered structure of compound 1 can undergo a crystal-to-crystal network reassembly, with the formation of the 3D network structure of compound 2 under dehydration conditions. Variable temperature and field magnetic studies reveal the existence of a distinct ferromagnetic interaction between Cu(2+) ions as the result of distinct syn-anti carboxylate bridging coordination modes.

  11. Tuning the structure and magnetism of heterometallic sodium(1+)-cobalt(2+) formate coordination polymers by varying the metal ratio and solvents.

    PubMed

    Zhao, Jiong-Peng; Han, Song-De; Zhao, Ran; Yang, Qian; Chang, Ze; Bu, Xian-He

    2013-03-18

    Three new heterometallic formate coordination polymers formulated as [Na2Co(HCOO)4]∞ (1), [NaCo(HCOO)3]∞ (2), and [Na2Co7(HCOO)16]∞ (3) were obtained by adjusting the solvent and ratio of the reactants. In 1, a (4,4) cobalt formate layer is formed and the sodium ions connect the layers to form a three-dimensional (3D) framework. In 2, each formate ligand binds two Co(2+) and two Na(+) ions with a syn,syn,anti,anti coordination mode to form a chrial network with 4,6-connected topology. 3 is a Na(+)-ion-linked 3D framework based on the cobalt formate layer, which has a 10-membered metal ring. Magnetic studies indicate the existence of ferromagnetic interactions between adjacent Co(2+) ions in 1, while dominating antiferromagnetic couplings in 2 and 3.

  12. A new linear bismuth coordination polymer based on 1,10-phenanthroline-2,9-dicarboxylic acid: ionothermal synthesis, crystal structure and fluorescence properties.

    PubMed

    Feng, Yu-Quan; Hu, Yu-Long; Wang, Hong-Wei; Cao, Feng-Pu

    2015-08-01

    A new linear bismuth(III) coordination polymer, catena-poly[[chloridobismuth(III)]-μ3-1,10-phenanthroline-2,9-dicarboxylato-κ(6)O(2):O(2),N(1),N(10),O(9):O(9)], [Bi(C14H6N2O4)Cl]n, has been obtained by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR spectroscopy, thermal stability studies and single-crystal X-ray diffraction. The structure is constructed by Bi(C14H6N2O4)Cl fragments in which each Bi(III) centre is seven-coordinated by one Cl atom, four O atoms and two N atoms. The coordination geometry of the Bi(III) cation is distorted pentagonal-bipyramidal (BiO4N2Cl), with one bridging carboxylate O atom and one Cl atom located in the axial positions. The Bi(C14H6N2O4)Cl fragments are further extended into a one-dimensional linear polymeric structure via subsequent but different centres of symmetry (bridging carboxylate O atoms). Neighbouring linear chains are assembled via weak C-H···O and C-H···Cl hydrogen bonds, forming a three-dimensional supramolecular architecture. Intermolecular π-π stacking interactions are observed, with centroid-to-centroid distances of 3.678 (4) Å, which further stabilize the structure. In addition, the solid-state fluorescence properties of the title coordination polymer were investigated. PMID:26243414

  13. Synthesis, Structure and Spectroscopy Study of a 1D Copper Coordination Polymer Based on a Carboxybenzyl Viologen Ligand and SCN-Anion.

    PubMed

    Qiu, Li-xia; Wan, Fang; Zhu, Bin-bin; Sun, Yan-qiong; You, Yi; Chen, Yi-ping

    2015-05-01

    A zwitterionic viologen derivative ligand, 1,1'-bis(4-carboxybenzyl)-4 4'-bipyridinium dichloride (H2BpybcCl2) as a multifunctional ligand, has been synthesized incorporating a 4,4'-bipyridine core with two carboxylate groups as a. building block, specifically designed for the rational construction of metal-organic frameworks. H2BpybcCl2 ligand is a multifunctional ligand that contains viologen's specific functions and carboxylate coordination groups. The coordination polymers of viologen carboxylate with copper thiocyanate are not reported to date. A novel copper coordination polymer, [Cu(SCN)2 (Bpybc)] (I) was by solution diffusion method and characterized by single-crystal X-ray diffraction, XRD, elemental analyses, IR spectroscopy, UV-Vis DRS, TG analysis and liquid-state luminescent properties. Compound I crystallized in the monoclinic system with C2/c space group. Crystal data for complex I is as follow: a=19. 508(4) A, b=9. 474(2) Å, c =16. 963(3) Å, α=90°, β=124. 92(3)°, γ=90°. Two SCN-anions were coordinated to the Cu2+ cation forming a [Cu(SCN)2] unit. Complex I was built up by [Cu(SCN)2] units bridged sequentially by ladder-shaped Bpybc ligands to form one-dimensional zigzag chains running along the [203] direction. The chains were held together by π-π interaction between the pyridine rings and phenyl rings, thus yielding a 3-D extended supramolecular network. The UV-Visible absorption spectra show the absorption bands of π-π* transitions of Bpybc ligands and d-->d transition of Cu2+. The liquid-state luminescent property of compound I was investigated at room temperature. Attractively, the complex exhibits strong blue emission peak at 533 nm (λEx=360 nn) that can be assigned to intraligand transition of Bpybc ligand when it was excited at 360 nm. PMID:26415457

  14. A new linear bismuth coordination polymer based on 1,10-phenanthroline-2,9-dicarboxylic acid: ionothermal synthesis, crystal structure and fluorescence properties.

    PubMed

    Feng, Yu-Quan; Hu, Yu-Long; Wang, Hong-Wei; Cao, Feng-Pu

    2015-08-01

    A new linear bismuth(III) coordination polymer, catena-poly[[chloridobismuth(III)]-μ3-1,10-phenanthroline-2,9-dicarboxylato-κ(6)O(2):O(2),N(1),N(10),O(9):O(9)], [Bi(C14H6N2O4)Cl]n, has been obtained by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR spectroscopy, thermal stability studies and single-crystal X-ray diffraction. The structure is constructed by Bi(C14H6N2O4)Cl fragments in which each Bi(III) centre is seven-coordinated by one Cl atom, four O atoms and two N atoms. The coordination geometry of the Bi(III) cation is distorted pentagonal-bipyramidal (BiO4N2Cl), with one bridging carboxylate O atom and one Cl atom located in the axial positions. The Bi(C14H6N2O4)Cl fragments are further extended into a one-dimensional linear polymeric structure via subsequent but different centres of symmetry (bridging carboxylate O atoms). Neighbouring linear chains are assembled via weak C-H···O and C-H···Cl hydrogen bonds, forming a three-dimensional supramolecular architecture. Intermolecular π-π stacking interactions are observed, with centroid-to-centroid distances of 3.678 (4) Å, which further stabilize the structure. In addition, the solid-state fluorescence properties of the title coordination polymer were investigated.

  15. Two new Cu(ii) and La(iii) 2D coordination polymers, synthesis and in situ structural analysis by X-ray diffraction.

    PubMed

    Lundvall, F; Wragg, D S; Dietzel, P D C; Fjellvåg, H

    2016-08-01

    Two new coordination polymers were synthesized solvothermally using 4,4'-dimethoxy-3,3'-biphenyldicarboxylic acid (H2dmbpdc), and di- and trivalent metal salts (Cu(NO3)2·2.5H2O and La(NO3)3·6H2O). Their structures were determined by single-crystal X-ray diffraction analysis, and their thermal stability was evaluated by thermogravimetric analysis. The copper compound Cu(dmbpdc)(DMF; N,N-dimethylformamide), CPO-71-Cu, is based on the well known copper acetate paddlewheel secondary building unit. The asymmetric unit comprises one copper cation with one DMF molecule and one linker molecule coordinated. The lanthanum compound La2(dmbpdc)3(DMF)(H2O)3, CPO-72-La, is formed from a dimer of nine-coordinate, edge sharing lanthanum cations. To this dimer, three water molecules and one DMF molecule are coordinated in an ordered fashion. In addition, the asymmetric unit contains three crystallographically unique linker molecules. Both CPO-71-Cu and CPO-72-La form two-dimensional layered structures, and topological analyses reveal sql topologies with point symbol 4(4)·6(2) and vertex symbol 4·4·4·4·6(2)·6(2). The thermal behavior of CPO-71-Cu was investigated in an in situ structural analysis by variable temperature powder- and single-crystal X-ray diffraction. PMID:27469613

  16. Nickel(II) and copper(II) coordination polymers with 1,2-bis(tetrazol-1-yl)ethane and thiocyanate: Structure, supramolecular isomerism and magnetism

    NASA Astrophysics Data System (ADS)

    Liu, Pei-Pei; Wang, Yan-Qin; Tian, Chun-Yan; Peng, Hui-Qi; Gao, En-Qing

    2009-02-01

    Two heteroleptic coordination polymers with the flexible 1,2-bis(tetrazol-1-yl)ethane (btze) ligand, [Ni(btze) 2(SCN) 2] n ( 1) and [Cu(btze)(SCN) 2] n ( 2), have been synthesized in presence of thiocyanate. Compound 1 is composed of 1D chains with double btze bridges in the V-shaped gauche conformation, while 2 exhibits 2D coordination networks in which 1D chains with double N, S-thiocyanate bridges are cross-linked by btze bridges in the Z-shaped transoid conformation. In both compounds, the coordination motifs are stacked into 3D architectures through S···S and C-H···N interactions. The structures of 1 and a previously reported compound illustrate an interesting type of supramolecular isomerism. The two isomers exhibit almost identical 1D coordination structure and 2D hydrogen bonded superstructure, and the difference lies only in the interlayer packing associated with S···S contacts. Compound 2 exhibits weak antiferromagnetic interactions with J = 0.29 cm -1, consistent with the structural observation that the thiocyanate bridge adopts an equatorial-axial disposition between Cu(II) ions.

  17. Magneto-structural versatility of copper(II)-3-phenylpropionate coordination polymers with N-donor coligands.

    PubMed

    de Campos, Nathália R; Ribeiro, Marcos A; Oliveira, Willian X C; Reis, Daniella O; Stumpf, Humberto O; Doriguetto, Antônio C; Machado, Flávia C; Pinheiro, Carlos B; Lloret, Francesc; Julve, Miguel; Cano, Joan; Marinho, Maria V

    2016-01-01

    A novel series of copper(II) coordination polymers [Cu2(O2CC8H9)4(pyz)]n (1), [Cu2(O2CC8H9)4(dps)]n (2), {[Cu(O2CC8H9)2(dps)(H2O)]·H2O}n (3), {[NaCu(O2CC8H9)2(bpm)(NO3)]·H2O}n (4), and [Cu4(O2CC8H9)6(OH)2(bpp)2]n (5) [O2CC8H9− = 3-phenylpropionate anion, pyz = pyrazine, dps = di(4-pyridyl)sulfide, bpm = 2,2′-bipyrimidine, and bpp = 1,3-bis(4-pyridyl)propane] have been synthesized and magneto-structurally investigated. Compounds 1 and 2 belong to a large group of copper(II) carboxylates where bis-monodentate pyz (1) and dps (2) ligands connect the paddle-wheel [CuII2(μ-O2CC8H9)4] units leading to alternating copper(II) chains. The structure of 3 consists of uniform chains of trans-[CuII(O2CC8H9)2] units linked by the bis-monodentate dps ligand. Compound 4 consists of heterobimetallic chains where [NaI2CuII2(μ-O2CC8H9)4(NO3)2] units are doubly bridged by bis-bidentate bpm ligands. Compound 5 is also a chain compound whose structure is made up by tetranuclear [CuII4(μ3-OH)2(μ-O2CC8H9)4(O2CC8H9)2] units which are doubly bridged by bis-monodentate bpp ligands. The magnetic properties were investigated in the temperature range 1.8–300 K. Strong antiferromagnetic interactions across the quadruple syn–syn carboxylate are observed in 1 and 2 [J = −378 (1) and −348 cm−1 (2)] whereas a weak ferromagnetic coupling through the double out-of-plane oxo(carboxylate) bridge occurs in 4 [J = +2.66 cm−1], the spin Hamiltonian being defined as H = −JS1·S2 with S1 = S2 = SCu = 1/2. A quasi Curie law is observed for 3 (θ = −0.36 cm−1), the bis-monodentate dps ligand being a very poor mediator of magnetic interactions. The analysis of the magnetic properties of 5 is quite complex because of the presence of two crystallographically independent tetracopper(II) units with single-μ-hydroxo, di-μ-hydroxo, μ3-hydroxo and single-μ-hydroxo plus double syn,syn carboxylate bridges in each one. The nature and values of the magnetic couplings for 5 obtained by

  18. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    PubMed

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems. PMID:26961352

  19. Dicynamide bridged two new zig-zag 1-D Zn(II) coordination polymers of pyrimidine derived Schiff base ligands: Synthesis, crystal structures and fluorescence studies

    NASA Astrophysics Data System (ADS)

    Konar, Saugata

    2015-07-01

    Two new zigzag 1-D polymeric Zn(II) coordination polymers {[Zn(L1)(μ1,5-dca)](H2O)}n (1), {[Zn(L2)(μ1,5-dca)](ClO4)}n (2) of two potentially tridentate NNO-, NNN-, donor Schiff base ligands [2-(2-(4,6-dimethylpyrimidin-2-yl)hydrazono)methyl)phenol] (L1), [1-(4,6-dimethylpyrimidin-2-yl)-2-(dipyridin-2ylmethylene)hydrazine] (L2) have been synthesized and characterized by elemental analyses, IR and 1H NMR, fluorescence spectroscopy and single crystal X-ray crystallography. The dicyanamide ions act as linkers (μ1,5 mode) in the formation of these coordination polymers. Both the complexes 1 and 2 have same distorted square pyramidal geometry around the Zn(II) centres. The weak forces like π⋯π, Csbnd H⋯π, anion⋯π interactions lead to various supramolecular architectures. Complex 1 shows high chelation enhanced fluorescence compared to that of 2. The fluorescence spectral changes observed high selectivity towards Zn(II) over other metal ions such as Mn(II), Co(II), Ni(II), Cu(II).

  20. A new one-dimensional coordination polymer of 5-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)isophthalic acid with manganese.

    PubMed

    Wang, Jing; Jia, Chunmei; Feng, Xiao; Yuan, Wenbing

    2015-09-01

    The coordination polymer catena-poly[[(dimethylformamide-κO)[μ3-5-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)isophthalato-κ(4)O(1),O(1'):O(3):O(3')](methanol-κO)manganese(III)] dimethylformamide monosolvate], {[Mn(C40H23NO6)(CH3OH)(C3H7NO)]·C3H7NO}n, has been synthesized from the reaction of 5-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)isophthalic acid and manganese(II) acetate tetrahydrate in a glass tube at room temperature by solvent diffusion. The Mn(II) centre is hexacoordinated by two O atoms from one chelating carboxylate group, by two O atoms from two monodentate carboxylate groups and by one O atom each from a methanol and a dimethylformamide (DMF) ligand. The single-crystal structure crystallizes in the triclinic space group P\\overline{1}. Moreover, the coordination polymer shows one-dimensional 2-connected {0} uninodal chain networks, and free DMF molecules are connected to the chains by O-H···O hydrogen bonds. The thermogravimetric and photoluminescent properties of the compound have also been investigated.

  1. An integrated logic system for time-resolved fluorescent "turn-on" detection of cysteine and histidine base on terbium (III) coordination polymer-copper (II) ensemble.

    PubMed

    Xue, Shi-Fan; Lu, Ling-Fei; Wang, Qi-Xian; Zhang, Shengqiang; Zhang, Min; Shi, Guoyue

    2016-09-01

    Cysteine (Cys) and histidine (His) both play indispensable roles in many important biological activities. An enhanced Cys level can result in Alzheimer's and cardiovascular diseases. Likewise, His plays a significant role in the growth and repair of tissues as well as in controlling the transmission of metal elements in biological bases. Therefore, it is meaningful to detect Cys and His simultaneously. In this work, a novel terbium (III) coordination polymer-Cu (II) ensemble (Tb(3+)/GMP-Cu(2+)) was proposed. Guanosine monophosphate (GMP) can self-assemble with Tb(3+) to form a supramolecular Tb(3+) coordination polymer (Tb(3+)/GMP), which can be suited as a time-resolved probe. The fluorescence of Tb(3+)/GMP would be quenched upon the addition of Cu(2+), and then the fluorescence of the as-prepared Tb(3+)/GMP-Cu(2+) ensemble would be restored again in the presence of Cys or His. By incorporating N-Ethylmaleimide and Ni(2+) as masking agents, Tb(3+)/GMP-Cu(2+) was further exploited as an integrated logic system and a specific time-resolved fluorescent "turn-on" assay for simultaneously sensing His and Cys was designed. Meanwhile it can also be used in plasma samples, showing great potential to meet the need of practical application. PMID:27343597

  2. A new one-dimensional coordination polymer of 5-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)isophthalic acid with manganese.

    PubMed

    Wang, Jing; Jia, Chunmei; Feng, Xiao; Yuan, Wenbing

    2015-09-01

    The coordination polymer catena-poly[[(dimethylformamide-κO)[μ3-5-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)isophthalato-κ(4)O(1),O(1'):O(3):O(3')](methanol-κO)manganese(III)] dimethylformamide monosolvate], {[Mn(C40H23NO6)(CH3OH)(C3H7NO)]·C3H7NO}n, has been synthesized from the reaction of 5-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)isophthalic acid and manganese(II) acetate tetrahydrate in a glass tube at room temperature by solvent diffusion. The Mn(II) centre is hexacoordinated by two O atoms from one chelating carboxylate group, by two O atoms from two monodentate carboxylate groups and by one O atom each from a methanol and a dimethylformamide (DMF) ligand. The single-crystal structure crystallizes in the triclinic space group P\\overline{1}. Moreover, the coordination polymer shows one-dimensional 2-connected {0} uninodal chain networks, and free DMF molecules are connected to the chains by O-H···O hydrogen bonds. The thermogravimetric and photoluminescent properties of the compound have also been investigated. PMID:26322606

  3. Assembly, structures and properties of four Cu(II) coordination polymers based on a semi-rigid bis-pyridyl-bis-amide ligand and different polycarboxylates

    NASA Astrophysics Data System (ADS)

    Wang, Xiu-Li; Luan, Jian; Lin, Hong-Yan; Lu, Qi-Lin; Le, Mao; Liu, Guo-Cheng

    2014-09-01

    Four new Cu(II) coordination polymers, namely, [Cu(3-bpah)(1,4-NDC)(H2O)]·3H2O (1), [Cu2(3-bpah)(1,4-NDC)2]·(1,4-H2NDC)·3H2O (2), [Cu(3-bpah)(3-NIP)] (3), [Cu(3-bpah)(1,3,5-HBTC)]·2H2O (4), where 3-bpah = N,N‧-bis(3-pyridinecarboxamide)-1,2-cyclohexane, 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid, 3-H2NIP = 3-nitrophthalic acid, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid, have been synthesized under hydrothermal conditions. The structures of 1-4 have been determined by single crystal X-ray diffraction and were further characterized by infrared spectroscopy (IR) and thermogravimetric analyses (TGA). Complex 1 displays a 1D double strand. Complex 2 shows a 3D α-Po framework with 1,4-H2NDC guest molecules inside the cages. Complex 3 reveals a 2D wave-like network. Complex 4 exhibits a 2D sql topology. The structural discrepancies of complexes 1-4 imply that the O-donor ancillary ligands play an important role in the formation of the resultant structures of the title coordination polymers. The fluorescent, electrochemical and photocatalytic properties of complexes 1-4 have been studied.

  4. Self assembly of sandwich-layered 2D silver(I) coordination polymers stabilized by argentophilic interactions: Synthesis, crystal structures and ab initio intramolecular energetics

    NASA Astrophysics Data System (ADS)

    Zorlu, Yunus; Can, Hatice

    2014-11-01

    Two different two-dimensional silver(I) coordination polymers, namely {[Ag2(dcpa)}n (1) and {[Ag2(ma)]}n (2), where dcpa = 4,5-dichlorophthalate; ma = maleate, were synthesized and structurally analyzed by single crystal X-ray diffraction technique. Complexes 1 and 2 represent 2D coordination polymer with metal-organic sandwich type. Two independent Ag(I) ions in both complexes are linked to constructed 2D layer by μ8-η3:η2:η2:η1 (for complex 1) and μ8-η3:η3:η2:η2 (for complex 2) carboxylate bridging fashions. The 2D layers of 1 are further extended into a three-dimensional (3D) supramolecular network by weak Cl⋯Cl interactions while 2D layers of 2 are linked by weak CH⋯O interactions into a 3D supramolecular framework. These two complexes exhibit considerable short Ag-Ag argentophilic interactions. The long-range corrected density functional theory (DFT) method was used to investigate intramolecular energetics, which are responsible for these 2D structures. Natural bond orbital (NBO) analysis with long-range corrected DFT method assists to understand these intramolecular interactions.

  5. Graphene oxide coated coordination polymer nanobelt composite material: a new type of visible light active and highly efficient photocatalyst for Cr(VI) reduction.

    PubMed

    Shi, Gui-Mei; Zhang, Bin; Xu, Xin-Xin; Fu, Yan-Hong

    2015-06-28

    A visible light active photocatalyst was synthesized successfully by coating graphene oxide (GO) on a coordination polymer nanobelt (CPNB) using a simple colloidal blending process. Compared with neat CPNB, the resulting graphene oxide coated coordination polymer nanobelt composite material (GO/CPNB) exhibits excellent photocatalytic efficiency in the reduction of K2Cr2O7 under visible light irradiation. In the composite material, GO performs two functions. Firstly, it cuts down the band gap (E(g)) of the photocatalyst and extends its photoresponse region from the ultraviolet to visible light region. Secondly, GO exhibits excellent electron transportation ability that impedes its recombination with holes, and this can enhance photocatalytic efficiency. For GO, on its surface, the number of functional groups has a great influence on the photocatalytic performance of the resulting GO/CPNB composite material and an ideal GO"coater" to obtain a highly efficient GO/CPNB photocatalyst has been obtained. As a photocatalyst that may be used in the treatment of Cr(VI) in wastewater, GO/CPNB exhibited outstanding stability during the reduction of this pollutant.

  6. Two interpenetrating Cu{sup II}/Ni{sup II}-coordinated polymers based on an unsymmetrical bifunctional N/O-tectonic: Syntheses, structures and magnetic properties

    SciTech Connect

    Liu, Yong-Liang; Wu, Ya-Pan; Li, Dong-Sheng; Dong, Wen-Wen; Zhou, Chun-Sheng

    2015-03-15

    Two new interpenetrating Cu{sup II}/Ni{sup II} coordination polymers, based on a unsymmetrical bifunctional N/O-tectonic 3-(pyrid-4′-yl)-5-(4″-carbonylphenyl)-1,2,4-triazolyl (H{sub 2}pycz), ([Cu-(Hpycz){sub 2}]·2H{sub 2}O){sub n} (1) and ([Ni(Hpycz){sub 2}]·H{sub 2}O){sub n} (2), have been solvothermally synthesized and structure characterization. Single crystal X-ray analysis indicates that compound 1 shows 2-fold parallel interpenetrated 4{sup 4}-sql layers with the same handedness. The overall structure of 1 is achiral—in each layer of doubly interpenetrating nets, the two individual nets have the opposite handedness to the corresponding nets in the adjoining layers—while 2 features a rare 8-fold interpenetrating 6{sup 6}-dia network that belongs to class IIIa interpenetration. In addition, compounds 1 and 2 both show similar paramagnetic characteristic properties. - Graphical abstract: Two new Cu(II)/Ni(II) coordination polymers present 2D parallel 2-fold interpenetrated 4{sup 4}-sql layers and a rare 3D 8-fold interpenetrating 6{sup 6}-dia network. In addition, magnetic susceptibility measurements show similar paramagnetic characteristic for two complexes. - Highlights: • A new unsymmetrical bifunctional N/O-tectonic as 4-connected spacer. • A 2-fold parallel interpenetrated sql layer with the same handedness. • A rare 8-fold interpenetrating dia network (class IIIa)

  7. Effect of substituent on structures and catalytic properties of cobalt(II) isophthalate coordination polymers with a semi-rigid bis(benzimidazole)

    NASA Astrophysics Data System (ADS)

    Zhang, Xu; Meng, Xiang-Li; Huang, Cui-Miao; Cui, Guang-Hua

    2015-11-01

    Three Co(II) coordination polymers based on flexible bis(2-dimethylbenzimidazole) and the derivatives of the familiar isophthalate co-ligands, namely [Co(L)(ip)]n (1), [Co2(L)2(nip)2]n (2) and [Co2(L)2(tbip)2·2H2O]n (3) (L = 1,2-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2ip = isophthalic acid, H2nip = 5-nitroisophthalic acid, H2tbip = 5-tert-butylisophthalic acid) have been synthesized by hydrothermal methods and characterized by elemental analyses, IR spectra, thermogravimetric analyses and single-crystal X-ray diffraction. Both complexes 1 and 2 exhibit a 2-fold interpenetrating 3D network with 66-dia topology, whereas complex 3 is bridged by the L and tbip2- ligands to form a rarely tri-nodal (3,3,5) layer with 3,3,5L18 topology. The results indicate that Co(II) mixed coordination polymers structurally modulated by the substituent effect of isophthalate-involved co-ligands. In addition, the fluorescence and catalytic activity of the complexes for the degradation of methyl orange by the sodium persulfate in a Fenton-like process have been investigated.

  8. The Enhancement on Proton Conductivity of Stable Polyoxometalate-Based Coordination Polymers by the Synergistic Effect of MultiProton Units.

    PubMed

    Li, Jing; Cao, Xue-Li; Wang, Yuan-Yuan; Zhang, Shu-Ran; Du, Dong-Ying; Qin, Jun-Sheng; Li, Shun-Li; Su, Zhong-Min; Lan, Ya-Qian

    2016-06-27

    Two novel polyoxometalate (POM)-based coordination polymers, namely, [Co(bpz)(Hbpz)][Co(SO4 )0.5 (H2 O)2 (bpz)]4 [PMo(VI) 8 Mo(V) 4 V(IV) 4 O42 ]⋅13 H2 O (NENU-530) and [Ni2 (bpz)(Hbpz)3 (H2 O)2 ][PMo(VI) 8 Mo(V) 4 V(IV) 4 O44 ]⋅8 H2 O (NENU-531) (H2 bpz=3,3',5,5'-tetramethyl-4,4'-bipyrazole), were isolated by hydrothermal methods, which represented 3D networks constructed by POM units, the protonated ligand and sulfate group. In contrast with most POM-based coordination polymers, these two compounds exhibit exceptional excellent chemical and thermal stability. More importantly, NENU-530 shows a high proton conductivity of 1.5×10(-3)  S cm(-1) at 75 °C and 98 % RH, which is one order of magnitude higher than that of NENU-531. Furthermore, structural analysis and functional measurement successfully demonstrated that the introduction of sulfate group is favorable for proton conductivity. Herein, the syntheses, crystal structures, proton conductivity, and the relationship between structure and property are presented.

  9. High-performance supercapacitor based on nitrogen-doped porous carbon derived from zinc(II)-bis(8-hydroxyquinoline) coordination polymer.

    PubMed

    Chen, Xiang Ying; Xie, Dong Hua; Chen, Chong; Liu, Jian Wei

    2013-03-01

    Nitrogen-doped porous carbon electrodes with remarkable specific capacitance have been fabricated by the rational carbonization of zinc(II)-bis(8-hydroxyquinoline) (abbr. Znq(2)) coordination polymer, and heating treatment with CO(NH(2))(2). The experimental results demonstrate that the mass ratio of carbon precursor and CO(NH(2))(2) plays a key role in the formation of porous carbon with various nitrogen content as well as specific surface areas and pore structures. The cyclic voltammetry and galvanostatic charge-discharge measurements show that the capacitive performance has been remarkably improved by doping with nitrogen. The specific capacitance of 219.2 F g(-1) is achieved at the current density of 1 A g(-1) with nitrogen-doped porous carbon, increasing up to ca. 56.8% compared to that with pristine porous carbon. The nitrogen-doped porous carbon electrode exhibits enhance capacitance retention as ca. 45.2% at 20 A g(-1) as well as cycling stability (ca. 7.6% loss after 3000 cycles). The present carbonization method as well as the nitrogen-doping method for porous carbon from coordination polymer can enrich the strategies for the production of carbon-based electrodes materials in the application of electrochemical capacitors.

  10. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    PubMed

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

  11. Heterobimetallic coordination polymers based on the [Pt(SCN)4]2- and [Pt(SeCN)4]2- building blocks.

    PubMed

    Kobayashi, Masayuki; Savard, Didier; Geisheimer, Andrew R; Sakai, Ken; Leznoff, Daniel B

    2013-05-01

    New complexes and the first coordination polymers containing [Pt(SCN)4](2-) of the type [M(L)x][Pt(SCN)4] (where L = 2,2'-bipyridine (bipy), x = 2, M = Co(II), Ni(II), Cu(II); L = ethylenediamine (en), x = 2, M = Ni(II), Cu(II); L = N,N,N',N'-tetramethylethylenediamine (tmeda), x = 1, M = Cu(II); L = 2,2';6',2″-terpyridine (terpy), x = 1, M = Mn(II), Co(II); L = 1,10-phenanthroline (phen), x = 2, M = Pb(II)) were prepared by reacting the appropriate metal-ligand cations with K2[Pt(SCN)4] and structurally characterized. [M(bipy)2Pt(SCN)4]2·2MeOH (M = Co (1), Cu (4)) consist of supramolecular tetranuclear distorted squares containing two [M(bipy)2](2+) and two [Pt(SCN)4](2+) units. [Cu(bipy)2(NCS)]2[Pt(SCN)4] (6) is a double salt of the [Pt(SCN)4](2-) anion and two [Cu(bipy)(NCS)](+) cations. [Cu(en)2Pt(SCN)4] (7, 8) are 1-D coordination polymers that are coordinated in either cis or trans fashion at the [Pt(SCN)4](2-) unit, for 7 and 8, respectively. Complexes [Cu(en)2Pt(SeCN)4] (9) and [Ni(en)2Pt(SCN)4] (10) are similar to 8 and 7, respectively, but complex 9 (prepared using ((n)Bu4N)2[Pt(SeCN)4]) also presents intermolecular Se-Se interactions which resulted in an increased dimensionality. Compounds [M(terpy)Pt(SCN)4] (M = Mn (11), Co (13)) involve 2-D sheets of [M(terpy)](2+) and [Pt(SCN)4](2-) units, whereas [Mn(terpy)2][Pt(SCN)4] (12) is a double salt of one [Mn(terpy)2](2+) unit and one [Pt(SCN)4](2-). [Cu(tmeda)Pt(SCN)4] (14) contains a five-coordinate Cu(2+) metal center coordinated to one tmeda ligand and three different [Pt(SCN)4](2-) units, resulting in 2-D sheets. [Pb(phen)2Pt(SCN)4] (15) contains an 8-coordinate Pb(2+) metal center coordinated to two phen ligands and four [Pt(SCN)4](2-), generating a 3-D network in the solid state. Structural correlations were established between the ancillary ligand, the choice of metal, the structure of the [Pt(SCN)4](2-) building block, and the resulting dimensionality of the coordination polymers. PMID:23574270

  12. Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

    PubMed

    Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

    2016-04-25

    Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface.

  13. Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

    PubMed

    Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

    2016-04-25

    Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface. PMID:27001452

  14. Multi-dimensional transition-metal coordination polymers of 4,4'-bipyridine-N,N'-dioxide: 1D chains and 2D sheets.

    PubMed

    Jia, Junhua; Blake, Alexander J; Champness, Neil R; Hubberstey, Peter; Wilson, Claire; Schröder, Martin

    2008-10-01

    Reaction of 4,4'-bipyridine -N, N' -dioxide (L) with a variety of transition-metal salts in MeOH affords a range of coordination polymer products. For the complexes [FeCl 3(mu-L)] infinity, 1, and ([Cu(L) 2(OHMe) 2(mu-L)].2PF 6. n(solv)) infinity, 2, 1D chain structures are observed, whereas ([Mn(mu-L) 3].2ClO 4) infinity, 3, and ([Cu(mu-L) 3].2BF 4) infinity, 4, both show 2D sheet architectures incorporating an unusual 3 (6)- hxl topology. The more common 4 (4)- sql topology is observed in [Cd(ONO 2) 2(mu-L) 2] infinity, 5, ([Cu(OHMe) 2(mu-L) 2].2ZrF 5) infinity, 6, ([Cu(L) 2(mu-L) 2].2EF 6) infinity ( 7 E = P; 8 E = Sb), and ([Et 4N][Cu(OHMe) 0.5(mu-L) 2(mu-FSiF 4F) 0.5].2SbF 6. n(solv)) infinity, 9. In 6, the [ZrF 5] (-) anion, formed in situ from [ZrF 6] (2-), forms 1D anionic chains ([ZrF 5] (-)) infinity of vertex-linked octahedra, and these chains thread through a pair of inclined polycatenated ([Cu(OHMe) 2(mu-L) 2] (2+)) infinity 4 (4)- sql grids to give a rare example of a triply intertwined coordination polymer. 9 also shows a 3D matrix structure with 4 (4)- sql sheets of stoichiometry ([Cu(L) 2] (2+)) infinity coordinatively linked by bridging [SiF 6] (2-) anions to give a structure of 5-c 4 (4).6 (6)- sqp topology. The mononuclear [Cu(L) 6].2BF 4 ( 10) and [Cd(L) 6].2NO 3 ( 11) and binuclear complexes [(Cu(L)(OH 2)) 2(mu-L) 2)].2SiF 6. n(solv), 12, are also reported. The majority of the coordination polymers are free of solvent and are nonporous. Thermal treatment of materials that do contain solvent results in structural disintegration of the complex structures giving no permanent porosity.

  15. Syntheses, crystal structures and properties of two 1-D cadmium(II) coordination polymers based on 1,1'-(1,3-propanediyl)bis-1H-benzimidazole

    SciTech Connect

    Yang Huaixia; Meng Xiangru; Liu Yun; Hou Hongwei Fan Yaoting; Shen Xiaoqing

    2008-09-15

    The combination of framework-builders 1,1'-(1,3-propanediyl)bis-1H-benzimidazole (pbbm), Cd(II) ion and framework-regulator ClO{sub 4}{sup -} or SO{sub 4}{sup 2-} provides two new coordination polymers [Cd(pbbm){sub 2}(ClO{sub 4}){sub 2}]{sub n}(1) and {l_brace}[Cd(pbbm)SO{sub 4}(H{sub 2}O){sub 2}].CH{sub 3}OH{r_brace}{sub n}(2). Both of them display 1-D chain framework, but their detailed structures are clearly different from each other. 1 displays a 1-D ribbon of rings framework, 2 features an interesting infinite 1-D looped chain structure composed of two kinds of rings, the smaller 8-membered ring and the larger 20-membered ring. The antimicrobial activities of the two polymers were tested by the agar diffusion method and the results indicated that they exhibited antimicrobial activities against bacterial strands. The measurement of the non-isothermal kinetics of the thermal decomposition of 2 reveals that there are at least three steps that occur in its decomposition process. - Graphical abstract: Two new Cd(II)-containing complexes have been synthesized and characterized by single-crystal X-ray diffraction. The antimicrobial activity and the non-isothermal kinetics of the thermal decomposition of the polymers were also investigated. Display Omitted.

  16. Anion-dependent construction of a series of fluorescent coordination polymers based on 1D zinc∩4,4‧-bis(imidazol-1-yl)-biphenyl substrates

    NASA Astrophysics Data System (ADS)

    Zou, Kang-Yu; Zou, Qian; Han, Tong; Liu, Yi-Chen; Wang, Jun-Jie; Zhang, Xue; Li, Zuo-Xi

    2016-03-01

    In this work, the rod-like ligand 4,4‧-bis(imidazol-1-yl)-biphenyl (bibp) has been utilized as a building block to carry out counterion effects on the structural diversities of coordination polymers. A series of new zinc complexes, [Zn(trans-bibp)Cl2]∞ (1), [Zn(trans-bibp)Br2]∞ (2), {[Zn(cis-bibp)(Ac)2]·(H2O)}∞ (3), [Zn(trans-bibp)SO4]∞ (4), {[Zn2(cis-bibp)2(ipa)2]·(H2O)}∞ (5, H2ipa=isophthalic acid) and {[Zn(trans-bibp)(cis-bibp)]·(ClO4)2(CHCl3)2(CH3OH)}∞ (6) have been successfully synthesized. Complexes 1 and 2 are iso-structural, which show a 1D W-type chain [Zn(trans-bibp)]∞. Complex 3 exhibits a 2D wave-like layer formed by the hydrogen bond among the 1D linear chain [Zn(cis-bibp)]∞. Complex 4 displays a 2D fish-bone lattice, which is generated from connecting the 1D W-type chain [Zn(trans-bibp)]∞ by the μ2-SO42- . Complex 5 presents an interesting 2D-3D 65·8 architecture, including two 1D chains [Zn(ipa)]∞ and [Zn(cis-bibp)]∞. Complex 6 demonstrates a 2D wave-like layer [Zn(trans-bibp)(cis-bibp)]∞. The structural diversities among 1-6 have been carefully discussed, and the role of counterion in the self-assembly of coordination polymer have also been well documented from the coordination affinity and bridging mode. Furthermore, the solid-state fluorescence properties of 1-6 at room temperature have been studied.

  17. A two-dimensional mixed-valence Cu(II)/Cu(I) coordination polymer constructed from 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate.

    PubMed

    Zhang, Li Yang; Lu, Li Ping; Feng, Si Si

    2016-08-01

    Coordination polymers are a thriving class of functional solid-state materials and there have been noticeable efforts and progress toward designing periodic functional structures with desired geometrical attributes and chemical properties for targeted applications. Self-assembly of metal ions and organic ligands is one of the most efficient and widely utilized methods for the construction of CPs under hydro(solvo)thermal conditions. 2-(Pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate (HPIDC(2-)) has been proven to be an excellent multidentate ligand due to its multiple deprotonation and coordination modes. Crystals of poly[aquabis[μ3-5-carboxy-2-(pyridin-3-yl)-1H-imidazole-4-carboxylato-κ(5)N(1),O(5):N(3),O(4):N(2)]copper(II)dicopper(I)], [Cu(II)Cu(I)2(C10H5N3O4)2(H2O)]n, (I), were obtained from 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylic acid (H3PIDC) and copper(II) chloride under hydrothermal conditions. The asymmetric unit consists of one independent Cu(II) ion, two Cu(I) ions, two HPIDC(2-) ligands and one coordinated water molecule. The Cu(II) centre displays a square-pyramidal geometry (CuN2O3), with two N,O-chelating HPIDC(2-) ligands occupying the basal plane in a trans geometry and one O atom from a coordinated water molecule in the axial position. The Cu(I) atoms adopt three-coordinated Y-shaped coordinations. In each [CuN2O] unit, deprotonated HPIDC(2-) acts as an N,O-chelating ligand, and a symmetry-equivalent HPIDC(2-) ligand acts as an N-atom donor via the pyridine group. The HPIDC(2-) ligands in the polymer serve as T-shaped 3-connectors and adopt a μ3-κ(2)N,O:κ(2)N',O':κN''-coordination mode, linking one Cu(II) and two Cu(I) cations. The Cu cations are arranged in one-dimensional -Cu1-Cu2-Cu3- chains along the [001] direction. Further crosslinking of these chains by HPIDC(2-) ligands along the b axis in a -Cu2-HPIDC(2-)-Cu3-HPIDC(2-)-Cu1- sequence results in a two-dimensional polymer in the (100) plane. The resulting (2,3)-connected net has a

  18. A two-dimensional mixed-valence Cu(II)/Cu(I) coordination polymer constructed from 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate.

    PubMed

    Zhang, Li Yang; Lu, Li Ping; Feng, Si Si

    2016-08-01

    Coordination polymers are a thriving class of functional solid-state materials and there have been noticeable efforts and progress toward designing periodic functional structures with desired geometrical attributes and chemical properties for targeted applications. Self-assembly of metal ions and organic ligands is one of the most efficient and widely utilized methods for the construction of CPs under hydro(solvo)thermal conditions. 2-(Pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate (HPIDC(2-)) has been proven to be an excellent multidentate ligand due to its multiple deprotonation and coordination modes. Crystals of poly[aquabis[μ3-5-carboxy-2-(pyridin-3-yl)-1H-imidazole-4-carboxylato-κ(5)N(1),O(5):N(3),O(4):N(2)]copper(II)dicopper(I)], [Cu(II)Cu(I)2(C10H5N3O4)2(H2O)]n, (I), were obtained from 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylic acid (H3PIDC) and copper(II) chloride under hydrothermal conditions. The asymmetric unit consists of one independent Cu(II) ion, two Cu(I) ions, two HPIDC(2-) ligands and one coordinated water molecule. The Cu(II) centre displays a square-pyramidal geometry (CuN2O3), with two N,O-chelating HPIDC(2-) ligands occupying the basal plane in a trans geometry and one O atom from a coordinated water molecule in the axial position. The Cu(I) atoms adopt three-coordinated Y-shaped coordinations. In each [CuN2O] unit, deprotonated HPIDC(2-) acts as an N,O-chelating ligand, and a symmetry-equivalent HPIDC(2-) ligand acts as an N-atom donor via the pyridine group. The HPIDC(2-) ligands in the polymer serve as T-shaped 3-connectors and adopt a μ3-κ(2)N,O:κ(2)N',O':κN''-coordination mode, linking one Cu(II) and two Cu(I) cations. The Cu cations are arranged in one-dimensional -Cu1-Cu2-Cu3- chains along the [001] direction. Further crosslinking of these chains by HPIDC(2-) ligands along the b axis in a -Cu2-HPIDC(2-)-Cu3-HPIDC(2-)-Cu1- sequence results in a two-dimensional polymer in the (100) plane. The resulting (2,3)-connected net has a

  19. Synthesis and crystal structure of a two-dimensional sodium coordination polymer of 4,4'-(diazenediyl)bis(1H-1,2,4-triazol-5-one).

    PubMed

    Guo, Jiajia; Cao, Wenli; Li, Shuailei; Miao, Kanghua; Song, Jirong; Huang, Jie

    2016-02-01

    The crystal engineering of coordination polymers has aroused interest due to their structural versatility, unique properties and applications in different areas of science. The selection of appropriate ligands as building blocks is critical in order to afford a range of topologies. Alkali metal cations are known for their mainly ionic chemistry in aqueous media. Their coordination number varies depending on the size of the binding partners, and on the electrostatic interaction between the ligands and the metal ions. The two-dimensional coordination polymer poly[tetra-μ-aqua-[μ4-4,4'-(diazenediyl)bis(5-oxo-1H-1,2,4-triazolido)]disodium(I)], [Na2(C4H2N8O2)(H2O)4]n, (I), was synthesized from 4-amino-1H-1,2,4-triazol-5(4H)-one (ATO) and its single-crystal structure determined. The mid-point of the imino N=N bond of the 4,4'-(diazenediyl)bis(5-oxo-1H-1,2,4-triazolide) (ZTO(2-)) ligand is located on an inversion centre. The asymmetric unit consists of one Na(+) cation, half a bridging ZTO(2-) ligand and two bridging water ligands. Each Na(+) cation is coordinated in a trigonal antiprismatic fashion by six O atoms, i.e. two from two ZTO(2-) ligands and the remaining four from bridging water ligands. The Na(+) cation is located near a glide plane, thus the two bridging O atoms from the two coordinating ZTO(2-) ligands are on adjacent apices of the trigonal antiprism, rather than being in an anti configuration. All water and ZTO(2-) ligands act as bridging ligands between metal centres. Each Na(+) metal centre is bridged to a neigbouring Na(+) cation by two water molecules to give a one-dimensional [Na(H2O)2]n chain. The organic ZTO(2-) ligand, an O atom of which also bridges the same pair of Na(+) cations, then crosslinks these [Na(H2O)2]n chains to form two-dimensional sheets. The two-dimensional sheets are further connected by intermolecular hydrogen bonds, giving rise to a stabile hydrogen-bonded network. PMID:26846504

  20. One-dimensional coordination polymers generated from a new triazole bridging ligand and HgX2 (X = Cl, Br and I): characterization and luminescent properties.

    PubMed

    Qin, Na; Zhao, Chao-Wei; Ma, Jian-Ping; Liu, Qi-Kui; Dong, Yu-Bin

    2012-06-01

    The new 4-amino-1,2,4-triazole asymmetric bridging ligand 4-amino-5-(pyridin-3-yl)-3-[4-(pyridin-4-yl)phenyl]-4H-1,2,4-triazole (L) has been used to generate three novel isomorphic one-dimensional coordination polymers, viz. catena-poly[[tris[dichloridomercury(II)]-bis{μ(3)-4-amino-5-(pyridin-3-yl)-3-[4-(pyridin-4-yl)phenyl]-4H-1,2,4-triazole}] acetonitrile monosolvate], {[Hg(3)Cl(6)(C(18)H(14)N(6))(2)]·CH(3)CN}(n), (I), and the bromido, {[Hg(3)Br(6)(C(18)H(14)N(6))(2)]·CH(3)CN}(n), (II), and iodido, {[Hg(3)I(6)(C(18)H(14)N(6))(2)]·CH(3)CN}(n), (III), analogs. The asymmetric ligand acts as a tridentate ligand to coordinate the three different Hg(II) centers (two of which are symmetry-related). Two ligands and two symmetry-related Hg(II) centers form centrosymmetric rectangular units which are linked into one-dimensional chains via the other unique Hg atoms, which sit on mirror planes. The chains are elaborated into a three-dimensional structure via interchain hydrogen bonds. The acetonitrile solvent molecules are located in ellipsoidal cavities. The luminescent character of these three coordination complexes was investigated in the solid state.

  1. Crystal structure of a mixed-ligand terbium(III) coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology.

    PubMed

    Kittipong, Chainok; Khemthong, Phailyn; Kielar, Filip; Zhou, Yan

    2016-01-01

    The title compound, poly[(μ 3-formato)(μ 4-oxalato)terbium(III)], [Tb(CHO2)(C2O4)] n , is a three-dimensional coordination polymer, and is isotypic with the La(III), Ce(III) and Sm(III) analogues. The asymmetric unit contains one Tb(III) ion, one formate anion (CHO2 (-)) and half of an oxalate anion (C2O4 (2-)), the latter being completed by application of inversion symmetry. The Tb(III) ion is nine-coordinated in a distorted tricapped trigonal-prismatic manner by two chelating carboxyl-ate groups from two C2O4 (2-) ligands, two carboxyl-ate oxygen atoms from another two C2O4 (2-) ligands and three oxygen atoms from three CHO2 (-) ligands, with the Tb-O bond lengths and the O-Tb-O bond angles ranging from 2.4165 (19) to 2.478 (3) Å and 64.53 (6) to 144.49 (4)°, respectively. The CHO2 (-) and C2O4 (2-) anions adopt μ 3-bridging and μ 4-chelating-bridging coordination modes, respectively, linking adjacent Tb(III) ions into a three-dimensional 12-connected fcu topology with point symbol (3(24).4(36).5(6)). The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

  2. o-, m-, and p-Pyridyl isomer effects on construction of 1D loop-and-chains: Silver(I) coordination polymers with Y-type tridentate ligands

    NASA Astrophysics Data System (ADS)

    Kim, Jeong Gyun; Cho, Yoonjung; Lee, Haeri; Lee, Young-A.; Jung, Ok-Sang

    2016-10-01

    Self-assembly of silver(I) hexafluorophosphate with unique Y-type tridentate ligands (2,6-bis[(2-picolinoyloxy-5-methylphenyl)methyl]-p-tolylpicolinate (o-L), 2-nicotinoyloxy- (m-L), and 2-isonicotinoyloxy- (p-L)) produces single crystals consisting of 1D loop-and-chain coordination polymers of [Ag(o-L)](PF6)·Me2CO·CHCl3, [Ag(m-L)](PF6)·Me2CO, and [Ag3(p-L)2](PF6)3·2H2O·2C2H5OH·4CH2Cl2 with quite different trigonal prismatic, trigonal, and linear silver(I) coordination geometry, respectively. Coordinating ability of the three ligands for AgPF6 is in the order of p-L > o-L > m-L. The solvate molecules of [Ag(o-L)](PF6)·Me2CO·CHCl3 can be removed, and be replaced reversibly in the order of acetone ≫ chloroform ≈ dichloromethane ≫ benzene, without destruction of its skeleton.

  3. Two three-dimensional coordination polymers of lead(II) with iminodiacetate and naphthalene-dicarboxylate anions: Synthesis, characterization and luminescence behavior

    SciTech Connect

    Hazari, Debdoot; Jana, Swapan Kumar; Fleck, Michel; Zangrando, Ennio; Dalai, Sudipta

    2014-11-15

    Two lead(II) compounds [Pb{sub 3}(idiac){sub 3}(phen){sub 2}(H{sub 2}O)]·2(H{sub 2}O) (1) and [Pb(ndc)]{sub n} (2), where H{sub 2}idiac=iminodiacetic acid, phen=1,10-phenanthroline and H{sub 2}ndc=naphthalene-2,6-dicarboxylic acid, have been synthesized and structurally characterized. Single crystal X-ray diffraction analysis showed that compound 1 is a discrete trinuclear complex (of two-fold symmetry) which evolves to a supramolecular 3D network via π–π interactions, while in compound 2 the naphthalene dicarboxylate anion act as a linker to form a three dimensional architecture, where the anion adopts a bis-(bidentate bridging) coordination mode connecting four Pb(II) centers. The photoluminescence property of the two complexes has been studied. - graphical abstract: Two new topologically different 1D coordination polymers formed by Pb{sub 4} clusters have been synthesized and characterized by x-ray analysis. The luminescence and thermal properties have been studied. - Highlights: • 1 is a trinuclear complex of Pb(II) growing to 3D network via weak interactions. • In 1, layers of (4,4) rhomboidal topology are identified. • In 2, the ndc anion adopts interesting bis-(bidentate bridging) coordination. • In 2, network is reinforced by C–H…π-ring interactions between the ndc rings.

  4. Synthesis, crystal structure and catalytic behavior of homo- and heteronuclear coordination polymers [M(tdc)(bpy)] (M2+ = Fe2+, Co2+, Zn2+, Cd2+; tdc2- = 2,5-thiophenedicarboxylate).

    PubMed

    Kettner, Florian; Worch, Christian; Moellmer, Jens; Gläser, Roger; Staudt, Reiner; Krautscheid, Harald

    2013-08-01

    A series of isostructural 3D coordination polymers (3)∞[M(tdc)(bpy)] (M(2+) = Zn(2+), Cd(2+), Co(2+), Fe(2+); tdc(2-) = 2,5-thiophenedicarboxylate; bpy = 4,4'-bipyridine) was synthesized and characterized by X-ray diffraction, thermal analysis, and gas adsorption measurements. The materials show high thermal stability up to approximately 400 °C and a solvent induced phase transition. Single crystal X-ray structure determination was successfully performed for all compounds after the phase transition. In the zinc-based coordination polymer, various amounts of a second type of metal ions such as Co(2+) or Fe(2+) could be incorporated. Furthermore, the catalytic behavior of the homo- and heteronuclear 3D coordination polymers in an oxidation model reaction was investigated.

  5. Organometallic Polymers.

    ERIC Educational Resources Information Center

    Carraher, Charles E., Jr.

    1981-01-01

    Reactions utilized to incorporate a metal-containing moiety into a polymer chain (addition, condensation, and coordination) are considered, emphasizing that these reactions also apply to smaller molecules. (JN)

  6. Ionothermal synthesis of two oxalate-bridged lanthanide(III) chains with slow magnetization relaxation by using a deep eutectic solvent.

    PubMed

    Meng, Yan; Liu, Jun-Liang; Zhang, Ze-Min; Lin, Wei-Quan; Lin, Zhuo-Jia; Tong, Ming-Liang

    2013-09-28

    Two novel isostructural oxalate-bridged lanthanide(III) chains, (choline)[Ln(ox)(H2O)3Cl]Cl·H2O (Ln = Dy/Er), were first obtained ionothermally by using a choline chloride-oxalic acid eutectic mixture as both solvent and structure-directing agent, both of which show field-induced slow relaxation of magnetization.

  7. Ionothermal synthesis of two oxalate-bridged lanthanide(III) chains with slow magnetization relaxation by using a deep eutectic solvent.

    PubMed

    Meng, Yan; Liu, Jun-Liang; Zhang, Ze-Min; Lin, Wei-Quan; Lin, Zhuo-Jia; Tong, Ming-Liang

    2013-09-28

    Two novel isostructural oxalate-bridged lanthanide(III) chains, (choline)[Ln(ox)(H2O)3Cl]Cl·H2O (Ln = Dy/Er), were first obtained ionothermally by using a choline chloride-oxalic acid eutectic mixture as both solvent and structure-directing agent, both of which show field-induced slow relaxation of magnetization. PMID:23903323

  8. Photocatalytic activity of transition-metal-ion-doped coordination polymer (CP): photoresponse region extension and quantum yields enhancement via doping of transition metal ions into the framework of CPs.

    PubMed

    Xu, Xin-Xin; Cui, Zhong-Ping; Gao, Xin; Liu, Xiao-Xia

    2014-06-21

    To improve photocatalytic activity of a coordination polymer (CP) in the visible light region, five different transition metal ions (Fe(3+), Cr(3+), Ru(3+), Co(2+) and Ni(2+)) were introduced into its framework through an ion-exchange process. Among all the resulting transition metal ion doped coordination polymers (TMI/CPs), the one doped with Fe(3+) took on the most excellent photocatalytic activity and the highest quantum yields in the visible light region, decomposing 94% Rhodamine B (RhB) in 8 hours. It can be attributed to the doping of Fe(3+), which reduced the band gap (Eg) of the original CP, facilitating photocatalysis of the obtained polymer. Compared with the coordination polymer with Fe(3+) as a dopant, products doped with other metal ions presented weaker photocatalytic activities in the visible light region, while under the irradiation of ultraviolet light, they showed favorable photocatalytic properties. The results suggest that to dope transition metal ions into the framework of CPs would be an ideal option for enhancing the photocatalytic activity of coordination polymers.

  9. Rational assembly of Pb(II)/Cd(II)/Mn(II) coordination polymers based on flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

    SciTech Connect

    Yang, Gao-Shan; Liu, Chong-Bo; Liu, Hong; Robbins, Julianne; Zhang, Z. John; Yin, Hong-Shan; Wen, Hui-Liang; Wang, Yu-Hua

    2015-05-15

    Six new coordination polymers, namely, [Pb(L)(H{sub 2}O)] (1), [Pb(L)(phen)] (2), [Pb{sub 2}(L){sub 2}(4,4′-bipy){sub 0.5}] (3), [Cd(L)(phen)] (4), [Cd(L)(4,4′-bipy)]·H{sub 2}O (5) and [Mn(L)(4,4′-bipy)]·H{sub 2}O (6) have been synthesized by the hydrothermal reaction of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) with Pb(II)/Cd(II)/Mn(II) in the presence of ancillary ligands 4,4′-bipyridine (4,4′-bipy) or 1,10-phenanthroline (phen). Complexes 1 and 4–6 exhibit 2-D structures, and complexes 2–3 display 3-D frameworks, of which L{sup 2−} ligands join metal ions to single-stranded helical chains of 1, 3–6 and double-stranded helical chains of 2. Complexes 2 and 3 also contain double-stranded Metal–O helices. Topology analysis reveals that complexes 1 and 4 both represent 4-connected sql net, 2 represents 6-connected pcu net, 3 exhibits a novel (3,12)-connected net, while 5 and 6 display (3,5)-connected gek1 net. The six complexes exhibit two kinds of inorganic–organic connectivities: I{sup 0}O{sup 2} for 1, 4–6, and I{sup 1}O{sup 2} for 2–3. The photoluminescent properties of 4–5 and the magnetic properties of 6 have been investigated. - Graphical abstract: Six new Pb(II)/Cd(II)/Mn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent and magnetic properties have been investigated. - Highlights: • Six novel M(II) coordination polymers with 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid and N-donor ligands. • Complexes 1–6 show diverse intriguing helical characters. • The luminescent properties of complexes 1–5 were investigated. • Complex 6 shows antiferromagnetic coupling.

  10. Color-tunable and white-light emission of one-dimensional L-di-2-thenoyltartaric acid mixed-lanthanide coordination polymers.

    PubMed

    Feng, Chang; Sun, Jing-Wen; Yan, Peng-Fei; Li, Yu-Xin; Liu, Tian-Qi; Sun, Qing-Yan; Li, Guang-Ming

    2015-03-14

    A series of L-di-2-thenoyltartaric acid lanthanide coordination polymers, namely, {[La2L3(CH3OH)6(H2O)]·CH3OH·H2O}n (1), {[Ln2L3(CH3OH)x(H2O)6−x]·aCH3OH·bH2O}n, [Ln = Eu (2), x = 2, a = 0.5, b = 0.25; Ln = Gd (3), x = 3, a = 1, b = 0; Ln = Tb (4), x = 2, a = 1, b = 0], {[(Eu0.037Tb0.963)2L3(CH3OH)2(H2O)4]·CH3OH·2.75H2O}n (5), {[(Eu0.051Tb0.406La0.543)2L3(CH3OH)2(H2O)4]·0.5CH3OH·2H2O}n (6), and {[(Eu0.068Tb0.363Gd0.569)2L3(CH3OH)3(H2O)3]·CH3OH·H2O}n (7), have been synthesized using facile reactions of H2L (H2L = L-di-2-thenoyltartaric acid) with LnCl3·6H2O under ambient temperature. X-ray crystallographic analysis reveals that complexes 1–4 are isostructural, featuring one-dimensional (1D) ladder-like chain structures, in which the Ln(3+) ions are bridged by the carboxylate groups of the ligands. The luminescent spectra in the solid state at room temperature reveal that complexes 2 and 4 exhibit the characteristic red and green luminescence of Eu(3+) and Tb(3+) ions, respectively, whereas complexes 1 and 3 display the blue emission of the ligand with a broad band centered at 422 nm. Notably, the mixed-lanthanide coordination polymers 5–7 exhibit color-tunable luminescence from yellow and white to blue upon variation of the excitation wavelength. It realizes color-tunable and white-light emission in 1D carboxylic acid mixed-lanthanide coordination polymers. PMID:25661972

  11. Metal coordination polymer derived mesoporous Co3O4 nanorods with uniform TiO2 coating as advanced anodes for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Geng, Hongbo; Ang, Huixiang; Ding, Xianguang; Tan, Huiteng; Guo, Guile; Qu, Genlong; Yang, Yonggang; Zheng, Junwei; Yan, Qingyu; Gu, Hongwei

    2016-01-01

    In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural stability during cycling.In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural

  12. Variations of structures and solid-state conductivity of isomeric silver(I) coordination polymers having linear and V-shaped thiophene-centered ditriazole ligands

    SciTech Connect

    Hu, Bin; Geng, Jiao; Zhang, Lie; Huang, Wei

    2014-07-01

    A pair of new linear and V-shaped acceptor–donor–acceptor (A−D−A) thiophene-centered ditriazole structural isomers, i.e., 2,5-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 1}) and 3,4-di(1H-1,2,4-triazol-1-yl)thiophene (L{sup 2}), has been synthesized and characterized. They are used as μ{sub 2}-bridging ligands to prepare a pair of silver(I) coordination polymers formulated as [Ag(L{sup 1})(NO{sub 3})]{sub n} (1) and [Ag(L{sup 2})(NO{sub 3})]{sub n} (2), which are also structural isomers at the supramolecular level. X-ray single-crystal diffraction analyses for 1 and 2 reveal that they exhibit the same one-dimensional (1D) coordination polymers but different structural architectures because of the distinguishable shape and configuration of isomeric ligands (L{sup 1} and L{sup 2}) and the alterations of the coordination numbers. More interestingly, compared with the free ligands, 1D silver(I) polymeric isomers 1 and 2 show significant enhancement of solid-state conductivity to different extents (1.42×10{sup 4} and 2.17×10{sup 3} times), where 6.96 times' enhancement of solid-state conductivity from 1 to 2 has been observed. The formation of Ag–N coordinative bonds and the configurational discrepancy of L{sup 1} and L{sup 2} are believed to play important roles in facilitating the electron transport between molecules, which can also be supported by Density Function Theory calculations of their band gaps. - Graphical abstract: A pair of linear and V-shaped isomeric thiophene-centered ditriazole ligands (L{sup 1}) and L{sup 2} are used to prepare a pair of silver(I) polymeric isomers (1 and 2), where significant enhancement of solid-state conductivity to different extents are observed originating from the distinguishable shape and configuration of isomeric ligands. - Highlights: • A pair of linear and V-shaped thiophene-centered ditriazole structural isomers is prepared. • They are used as µ{sub 2}-bridging ligands to prepare a pair of silver

  13. Crystal structures, fluorescent and magnetic properties of five new coordination polymers based on biphenyl-3,4 Prime ,5-tricarboxylic acid

    SciTech Connect

    Lu Yingli; Zhao Wenjie; Liu Yu; Liu Bin; Feng Xing; Tan Jinting; Li Xia; Yang Xuwu

    2012-08-15

    Five new coordination polymers, {l_brace}[Cd{sub 3}(bpt){sub 2}(DMF){sub 2}]{center_dot}(H{sub 2}O){sub 2}{r_brace}{sub n} (1), [Cd(Hbpt)(bipy){sub 0.5}(H{sub 2}O)]{sub n} (2), [Cd{sub 2}(bpt)(phen){sub 2}Cl]{sub n} (3), {l_brace}[Cu{sub 2}(bpt)(phen)({mu}{sub 2}-OH)(H{sub 2}O)]{center_dot}(H{sub 2}O){sub 2}{r_brace}{sub n} (4) and {l_brace}[Mn{sub 5}(Hbpt){sub 4}(phen){sub 4}({mu}{sub 2}-OH){sub 2}(H{sub 2}O){sub 2}]{center_dot}(H{sub 2}O){sub 2}(CH{sub 3}CN){sub 2}{r_brace}{sub n} (5) have been prepared through hydro(solvo)thermal reactions of H{sub 3}bpt (H{sub 3}bpt=biphenyl-3,4 Prime ,5-tricarboxylic acid) with different pyridyl-containing auxiliary ligands (bipy=4,4 Prime -bipyridine and phen=1,10-phenanthroline). Compound 1 represents a 3D ladder-like framework composed of rod-shaped infinite chains. In 2, the bridging ligand bipy links binuclear cadmium ions to generate a 2D layer. Compound 3 features a 1D ladder structure and further linked by {pi}-{pi} stacking interaction to form a 3D supramolecular network. Compound 4 exhibits a binodal 3-connected net which features the Schlafli symbol of (4{center_dot}8{sup 2}). Compound 5 contains trimetallic cluster and binuclear unite which are further linked by Hbpt ligand to form a 2D layer. Moreover, photoluminescent properties of compounds 1-3 were studied in the solid state. Magnetic susceptibility measurements indicate that compound 4 exhibits ferromagnetic exchange interactions, whereas compound 5 displays antiferromagnetic exchange interactions. - Graphical abstract: Five new coordination polymers have been prepared through reactions of H{sub 3}bpt with different pyridyl-containing auxiliary ligands. The bpt exhibits four new kinds of coordination modes with 'V or Y shape'. Highlights: Black-Right-Pointing-Pointer 1 represents a unique (4{center_dot}8)-connected network with a Schlafli symbol (4{sup 6})(4{sup 12}{center_dot}6{sup 12}{center_dot}8{sup 4}). Black-Right-Pointing-Pointer Compound 4 shows

  14. Metal-containing ligands for mixed-metal polymers: novel Cu(II)-Ag(I) mixed-metal coordination polymers generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O and silver(I) salts.

    PubMed

    Dong, Y B; Smith, M D; zur Loye, H C

    2000-05-01

    One Cu(II)-containing ligand and two Cu(II)-Ag(I) mixed-metal coordination polymers have been synthesized. [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O (1) was obtained as a molecular complex with two uncoordinated nitrogen donors by the reaction of 2-methylpyrazine-5-carboxylate sodium with CuCl(2).2H2O in water. Compound 1 crystallized in the triclinic space group P1, with a = 10.498(2) A, b = 11.000(2) A, c = 8.1424(16) A, alpha = 98.33(3) degrees, beta = 101.83(3) degrees, gamma = 66.68(3) degrees, and Z = 2. Reactions of 1 with silver(I) salts have been studied. Two Cu(II)-Ag(I) mixed-metal coordination polymers, namely, Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](BF4) (2) and Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](NO3) (3), have been generated by treating 1 with AgBF4 and AgNO3, respectively. Compound 2 crystallized in the monoclinic space group C2/c, with a = 25.827(5) A, b = 9.6430(19) A, c = 7.4525(15) A, beta = 94.74(3) degrees, and Z = 4. Compound 3 also crystallized in the monoclinic space group C2/c, with a = 25.855(5) A, b = 9.782(2) A, c = 7.1201(14) A, beta = 96.90(3) degrees, and Z = 4. The main structural feature in both 2 and 3 is a zigzag Cu(II)-Ag(I) mixed-metal chain, in which the alternating Cu(II) and Ag(I) centers are linked by 2-methylpyrazine-5-carboxylate spacers. The effect of the nitrate counterion was illustrated by compound 3, in which a novel [Ag+...NO3-] coordination chain has been found which acts as the connector to cross-link the one-dimensional zigzag chains into a three-dimensional network. In addition, an identical interchain O-H...O hydrogen bonding system has been found in both 2 and 3 and has been shown to play a significant role in directing the alignment of the one-dimensional mixed-metal polymer chains in the crystalline state. The magnetic susceptibilities of 2 and 3 were measured and found to follow the Curie law (mu eff = 1.85 for 2 and 1.83 for 3). PMID:11428114

  15. A new nano-scale manganese (II) coordination polymer constructed from semicarbazone Schiff base and dicyanamide ligands: Synthesis, crystal structure and DFT calculations

    NASA Astrophysics Data System (ADS)

    Farhadi, Saeed; Mahmoudi, Farzaneh; Simpson, Jim

    2016-03-01

    A new nano-structured Mn(II) coordination polymer [Mn(HL)(dca)(Cl)]n(1), [HL= Pyridine-2-carbaldehyde semicarbazone, dca= dicyanamide] has been synthesized by a sonochemical method and has been characterized by scanning electron microscopy, X-ray powder diffraction elemental analysis and IR spectroscopy. Single crystals of compound 1 was synthesized by slow evaporation method and was structurally characterised by single crystal X-ray diffraction. The single crystal structure shows one dimensional zig-zag chains with end-to-end dicyanamide-bridged ligand. A distorted octahedral geometry around the Mn2+centers was achieved by NNO atoms from HL, two nitrogen atoms of dicyanamide and one chlorine atom. Also for more details, the structure of 1, has been optimized by density functional theory (DFT calculations).

  16. Copper and cobalt coordination polymers based on isophthalate as bridging ligands and imidazole as capping ligands: Syntheses, crystal structures, spectroscopic characterization

    NASA Astrophysics Data System (ADS)

    Song, Jiang-Feng; Chen, Yan; Li, Zhi-Gang; Zhou, Rui-Sha; Xu, Xiao-Yu; Xu, Ji-Qing

    2007-10-01

    Two novel coordination polymers, {[Cu(ip)(Him) 2(DMF)]·H 2O} ( 1) and Co(ip)(Him) 2 ( 2), (ip = isophthalate, Him = imidazole) were prepared under hydrothermal conditions and their structures were determined by single-crystal X-ray diffraction. X-ray structural analysis reveals that 1-D zigzag metal-organic chains are connected to form a 3-D supramolecular framework in compounds 1 and 2 by hydrogen-bonding and π-π interaction or other intermolecular contacts. Infrared, UV-vis, and elemental analysis were performed to characterize the two compounds. The result of magnetic determination for compound 2 shows there exist antiferromagnetic interaction between magnetic centers.

  17. One Unique 1D Silver(I)-Bromide-Thiol Coordination Polymer Used for Highly Efficient Chemiresistive Sensing of Ammonia and Amines in Water.

    PubMed

    Wang, Fan; Wang, Yu-Ting; Yu, Hong; Chen, Jin-Xiang; Gao, Bin-Bin; Lang, Jian-Ping

    2016-09-19

    Reaction of AgBr with TabHPF6 (TabH = 4-(trimethylammonio)benzenethiol) readily produces a unique one-dimensional coordination polymer [(TabH)(AgBr2)]n (1), consisting of anionic chains [AgBr2]n(n-) with hydrogen bonds to TabH(+) cations. By examining its electrical resistance and stability upon exposure to ammonia and seven common organic amines in water under ambient conditions, compound 1 is found to exhibit good stability and reproducibly high sensitivity toward these analytes at low concentrations. Especially, it can selectively detect NH3 in water with the detection limit as low as 0.05 ppm. This chemiresistive sensing system has the potential for highly efficient monitoring of ammonia and amines responsible for water pollution, eutrophication, food contamination, and industrial hazards. PMID:27579781

  18. Crystal growth and characterization studies of novel luminescent 2D coordination polymer of lead-benzilate possessing edge sharing PbO6 polyhedra

    NASA Astrophysics Data System (ADS)

    Soumya Mol, U. S.; Drisya, R.; Satheesh Chandran, P. R.; Sudarsanakumar, M. R.; Suma, S.; Sudhadevi Antharjanam, P. K.

    2016-12-01

    Single crystals of a new coordination polymer of lead-benzilate, C28H21O6Pb·C2H5OH have been successfully grown by gel diffusion technique at room temperature. The colourless single crystals were obtained within a week. The crystal structure was elucidated using single crystal X-ray diffraction studies. The compound possesses a polymeric structure constructed from edge sharing PbO6 polyhedra. Single crystal X-ray diffraction analysis showed that the compound crystallizes in triclinic space group P-1. The grown crystals were further characterized by elemental analysis, FT-IR, UV-Visible and thermogravimetric analysis. The photoluminescent properties of the complex and the ligand were also investigated.

  19. Mercury coordination polymers with flexible ethane-1,2-diyl-bis-(pyridyl-3-carboxylate): Synthesis, structures, thermal and luminescent properties

    NASA Astrophysics Data System (ADS)

    Vallejos, Javier; Brito, Iván; Cárdenas, Alejandro; Llanos, Jaime; Bolte, Michael; López-Rodríguez, Matías

    2015-03-01

    The reaction of the flexible ligand, ethane-1,2-diyl-bis-(pyridyl-3-carboxylate), (L) with HgI2 and HgBr2 salts under the same experimental conditions leads to the formation of two coordination polymers with different motifs: {[Hg(L)(Br2)]}n(1) and {[Hg(L)(I2)]}n(2). In both compounds, the ligand, (L) acts in a μ2-N:N‧-bidentate fashion to link HgBr2 and HgI2 units to form a linear and helical chain motif, along [1 0 0] for (1) and [0 0 1] for (2). The ethylene moiety of (L) has gauche and trans conformation in compounds (1) and (2), respectively. The flexible conformation of L produces differences in the optical and crystal properties of the two compounds.

  20. Syntheses, structures and properties of two new coordination polymers based on D-camphoric acid and 2-phenyl-4,6-diamino-1,3,5-triazine

    NASA Astrophysics Data System (ADS)

    Lun, Huijie; Yang, Jinghe; Jin, Linyu; Cui, Sasa; Bai, Yanlong; Zhang, Xudong; Li, Yamin

    2015-05-01

    By hydrothermal method, two new coordination polymers [Co(ca)(phdat)]n (1), [Ni(ca)(phdat).0.125H2O]n (2) (H2ca=D-camphoric acid, phdat=2-phenyl-4,6-diamino-1,3,5-triazine) have been achieved and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isostructural, both of which exhibit two-dimensional layered network built up from paddle-wheel Co2(CO2)4/Ni2(CO2)4 SBUs by ca2- ligand. In the existence of π…π stacking interactions between triazine rings and phenyl rings, the 3D networks are constructed with the hanging phdat filled between the neighboring layers. Furthermore, compounds 1-2 exhibit antiferromagnetic behavior and compound 2 displays a good activity for methanol oxidation.

  1. Synthesis, characterisation and adsorption properties of a porous copper(II) 3D coordination polymer exhibiting strong binding enthalpy and adsorption capacity for carbon dioxide.

    PubMed

    Eckold, Pierre; Gee, William J; Hill, Matthew R; Batten, Stuart R

    2012-11-21

    The synthesis and characterisation of microporous coordination polymers containing copper(II) or cobalt(II) and 2-(pyridin-4-yl)malonaldehyde (Hpma) is described and the gas adsorption properties evaluated. Single-crystal X-ray structure determinations identified the structures as [M(pma)(2)]·2X (M = Cu, 1; Co, 2; X = MeOH, MeCN), which contain 3D networks with rutile topology and continuous 1D rectangular channels with diameters ranging from 3 to 4 Å. The materials exhibit low BET surface areas of 143 m(2) g(-1), but possess large capacities for carbon dioxide capture of 14.1 wt%. The small pore channels are shown to account for this, delivering a particularly strong binding enthalpy to adsorbed CO(2) of 38 kJ mol(-1), and a very large adsorption capacity relative to the low surface area.

  2. A Step-by-Step Assembly of a 3D Coordination Polymer in the Solid-State by Desolvation and [2+2] Cycloaddition Reactions.

    PubMed

    Medishetty, Raghavender; Tandiana, Rika; Wu, Jien; Bai, Zhaozhi; Du, Yonghua; Vittal, Jagadese J

    2015-08-17

    Two solid-state structural transformations that occur in a stepwise and a controlled manner are described. A combination of desolvation and cycloaddition reactions has been employed to synthesise a 3D coordination polymer (CP) from 1D CP [Cd(bdc)(4-spy)2 (H2 O)]⋅2 H2 O⋅2 DMF (bdc=1,4-benzenedicarboxylate, 4-spy=4-styrylpyridine) presumably via a 2D layered structure, [Cd2 (bdc)2 (4-spy)4 ]. In the absence of single crystals to follow the course of the photocycloaddition reaction, thermogravimetry, XAFS and NOESY NMR experiments were used to propose the formation of layered and pillared layered structures. Further, the present strategy enables us to synthesise new multidimensional architectures that are otherwise inaccessible by the self-assembly process. PMID:26150356

  3. Hydrothermal synthesis of Bismuth(III) coordination polymer and its transformation to nano α-Bi2O3 for photocatalytic degradation

    NASA Astrophysics Data System (ADS)

    Huang, Ya-Jing; Zheng, Yue-Qing; Zhu, Hong-Lin; Wang, Jin-Jian

    2016-07-01

    A new Bi(III) coordination polymer Bi2(Hpdc)2(pdc)2·2H2O (H2pdc=pyridine-2,6-dicarboxylic acid) was synthesized by hydrothermal method. Solid state thermal decomposition of this complex under 500 °C for 1 h led to the foliated Bi2O3 nanoparticles, which were then characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Comparative study on their photocatalytic activity toward the degradation of rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) in polluted water was explored, and the mechanism of these photocatalytic degradation was discussed. These results provided some interesting insights into their photocatalytic applications.

  4. Two interpenetrating CuII/NiII-coordinated polymers based on an unsymmetrical bifunctional N/O-tectonic: Syntheses, structures and magnetic properties

    NASA Astrophysics Data System (ADS)

    Liu, Yong-Liang; Wu, Ya-Pan; Li, Dong-Sheng; Dong, Wen-Wen; Zhou, Chun-Sheng

    2015-03-01

    Two new interpenetrating CuII/NiII coordination polymers, based on a unsymmetrical bifunctional N/O-tectonic 3-(pyrid-4‧-yl)-5-(4″-carbonylphenyl)-1,2,4-triazolyl (H2pycz), {[Cu-(Hpycz)2]·2H2O}n (1) and {[Ni(Hpycz)2]·H2O}n (2), have been solvothermally synthesized and structure characterization. Single crystal X-ray analysis indicates that compound 1 shows 2-fold parallel interpenetrated 44-sql layers with the same handedness. The overall structure of 1 is achiral-in each layer of doubly interpenetrating nets, the two individual nets have the opposite handedness to the corresponding nets in the adjoining layers-while 2 features a rare 8-fold interpenetrating 66-dia network that belongs to class IIIa interpenetration. In addition, compounds 1 and 2 both show similar paramagnetic characteristic properties.

  5. Syntheses, structures and properties of Mn(II), Zn(II) and Ag(I) coordination polymers with 2-(1,2,4-triazol-1-yl)acetate

    NASA Astrophysics Data System (ADS)

    Qian, Xin; Sun, Peng-Peng; Ding, Jian-Gang; Li, Bao-Long; Li, Han-Yan

    2013-01-01

    The self-assembly reaction of 2-(1,2,4-triazol-1-yl)acetic acid (Htza) with Mn(II), Zn(II) and Ag(I) salts gave three coordination polymers [Mn(tza)2]n (1), [Zn(tza)2]n (2) and [Ag3(tza)2(ClO4)]n (3). 1 has a (3,6)-connected CdCl2-type two-dimensional network. 2 is a neutral two-dimensional (4,4) network. However 3 shows the complicated two-dimensional undulated network. 2 and 3 exhibit blue luminescent emissions maxima at 420 and 437 nm, respectively in the solid state at room temperature. The thermal stability of 1, 2 and 3 were observed. The diffuse reflectance UV-vis spectroscopy of 1, 2 and 3 were measured.

  6. Nanoflakes of an aminoacid-based chiral coordination polymer: Synthesis, optical and electrochemical properties, and application in electrochemical sensing of H2O2

    NASA Astrophysics Data System (ADS)

    Zhou, Bo; Liang, Li-Mei; Yao, Jie

    2015-03-01

    Nanoflakes of an aminoacid-based chiral coordination polymer (CP), [Cu2(tyr)2(bipy)]n, were synthesized successfully in the presence of surfactant, as evidenced by the XRD and SEM results. UV-vis absorption spectrometry and fluorescence spectrometry were used to investigate the optical properties of the CP, which was found to be mainly attributed to the ligands, while the forming of the CP caused only slight change. On the other hand, Cu(II) ions acted as electrocatalytic active sites of the CP, as evidenced by cyclic voltammetry. The CP also showed good performance in the electrochemical sensing of H2O2: sensitivity of 85.6 mA mol-1 L cm-2, linear range of 1.0×10-5-7.69×10-3 M, detection limit of 1.0×10-5 M (S/N=3), and fast response in mere 5 s.

  7. Two novel coordination polymers constructed by the same mixed ligands of 1,3-bip and H2bpdc: Syntheses, structures and catalytic properties

    NASA Astrophysics Data System (ADS)

    Lu, Jiu-Fu; Wang, Min-Zhen; Liu, Zhi-Hong

    2015-10-01

    Two novel coordination polymers, namely [Co(1,3-bip)(bpdc)·0.5H2bpdc]n (1), [Cu(1,3-bip)(bpdc)·3H2O]n (2), where 1,3-bip = 1,3-bis(imidazol-1-yl)propane, H2bpdc = biphenyl-4,4‧-dicarboxylic acid, were synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction, powder XRD, FT-IR, TGA and elemental analysis techniques. Single crystal X-ray analysis revealed that complex 1 features a 3D → 3D fivefold interpenetrating framework. The structure of complex 2 displays a (4,4) grid layer which is further reinforced through strong H-bonding with lattice solvent molecules to form a 3D supramolecular framework. Furthermore, the complexes 1 and 2 exhibit catalytic properties on degradation of methyl orange in Fenton-like process.

  8. Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers.

    PubMed

    Vinogradova, Katerina A; Krivopalov, Viktor P; Nikolaenkova, Elena B; Pervukhina, Natalia V; Naumov, Dmitrii Yu; Boguslavsky, Evgenii G; Bushuev, Mark B

    2016-01-14

    Two pyrimidine-based ligands, 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(morpholino)pyrimidine () and 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-phenoxypyrimidine (), and a series of mixed-valence copper(i,ii) halide complexes, [Cu(L(2))2Br]2[Cu2Br4] (), [Cu(L(2))2Cl][CuCl2] (), and [Cu2L(3)Br3]n (), have been synthesized. The complex [Cu(L(2))2Br]2[Cu2Br4] was prepared by the reaction of with CuBr2 in a 1 : 1 molar ratio in MeCN. Its chlorido-analogue, the complex [Cu(L(2))2Cl][CuCl2], was synthesized by the reaction between , CuCl2 and CuCl in a 2 : 1 : 1 molar ratio in MeCN. The ligand acts as a chelating one. In the structures of the complexes [Cu(L(2))2Br]2[Cu2Br4] and [Cu(L(2))2Cl][CuCl2] the Cu(2+) ion is in the cationic part of the complex whereas the Cu(+) ion is located in the anionic part. The best way to synthesize the mixed-valence 1D coordination polymer [Cu2L(3)Br3]n is to react CuBr2 with in a 2 : 1 molar ratio in the MeCN/CHCl3 mixture on heating. In the structure of [Cu2L(3)Br3]n the ligand shows chelating/bridging tridentate coordination. This is the first example of the tridentate coordination of 4-(1H-pyrazol-1-yl)-6-R-pyrimidines. The striking difference between the coordination behavior of and (chelating bidentate vs. chelating/bridging coordination) is related with the possibility of rotation of the 6-phenoxy group around the C-O bond which makes the N(1) pyrimidine atom less sterically hindered, enabling it to participate in metal ion binding. Importantly, all copper ions in [Cu2L(3)Br3]n show similar tetrahedral environments, CuNBr3 and CuN2Br2, which is extremely rare for mixed-valence copper(i,ii) compounds. The ligands and show blue emission which is quenched upon their coordination to copper ions. The 1D coordination polymer [Cu2L(3)Br3]n shows high thermal stability and unusual solvent-occlusion properties. The role of the substituents favoring the formation of the mixed-valence copper(i,ii) complexes with 4-(1H-pyrazol-1-yl)-6-R

  9. Synthesis, structure and characterization of two copper(II) supramolecular coordination polymers based on a multifunctional ligand 2-amino-4-sulfobenzoic acid.

    PubMed

    Wei, Yan; Zhang, Lei; Wang, Meng-Jie; Chen, Si-Chun; Wang, Zi-Hao; Zhang, Kou-Lin

    2015-07-01

    Copper(II) coordination polymers have attracted considerable interest due to their catalytic, adsorption, luminescence and magnetic properties. The reactions of copper(II) with 2-amino-4-sulfobenzoic acid (H(2)asba) in the presence/absence of the auxiliary chelating ligand 1,10-phenanthroline (phen) under ambient conditions yielded two supramolecular coordination polymers, namely (3-amino-4-carboxybenzene-1-sulfonato-κO(1))bis(1,10-phenanthroline-κ(2)N,N')copper(II) 3-amino-4-carboxybenzene-1-sulfonate monohydrate, [Cu(C7H6N2O5S)(C12H8N2)2](C7H6N2O5S)·H2O, (1), and catena-poly[[diaquacopper(II)]-μ-3-amino-4-carboxylatobenzene-1-sulfonato-κ(2)O(4):O(4')], [Cu(C7H6N2O5S)(H2O)2]n, (2). The products were characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), solid-state UV-Vis spectroscopy and single-crystal X-ray diffraction analysis, as well as by variable-temperature powder X-ray diffraction analysis (VT-PXRD). Intermolecular π-π stacking interactions in (1) link the mononuclear copper(II) cation units into a supramolecular polymeric chain, which is further extended into a supramolecular double chain through interchain hydrogen bonds. Supramolecular double chains are then extended into a two-dimensional supramolecular double layer through hydrogen bonds between the lattice Hasba(-) anions, H2O molecules and double chains. Left- and right-handed 21 helices formed by the Hasba(-) anions are arranged alternately within the two-dimensional supramolecular double layers. Complex (2) exhibits a polymeric chain which is further extended into a three-dimensional supramolecular network through interchain hydrogen bonds. Complex (1) shows a reversible dehydration-rehydration behaviour, while complex (2) shows an irreversible dehydration-rehydration behaviour.

  10. Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

    SciTech Connect

    Ran, Xing-Rui; Wang, Ning; Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian; Long, Yi; Yue, Shan-Tang; Liu, Ying-Liang

    2015-05-15

    By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.

  11. A Zn(II) coordination polymer and its photocycloaddition product: syntheses, structures, selective luminescence sensing of iron(III) ions and selective absorption of dyes.

    PubMed

    Hu, Fei-long; Shi, Yi-Xiang; Chen, Huan-Huan; Lang, Jian-Ping

    2015-11-21

    One coordination polymer [Zn2(L)2(bpe)2(H2O)2] (1) (L = 4,4'-((1,2-phenylenebis(methylene))bis(oxy))dibenzoic acid; bpe = (E)-1,2-di(pyridin-4-yl)ethene) was prepared and structurally determined. Compound 1 has a chain structure in which its pair of bpe ligands is arranged in a head-to-tail manner with their C=C bonds being close enough for a [2 + 2] cycloaddition reaction. Upon exposure to UV light, compound 1 undergoes a single-crystal-to-single-crystal (SCSC) [2 + 2] photodimerization to generate one 2D coordination polymer [Zn(L)(rctt-tpcb)0.5(H2O)] (1a) (rctt (regio cis, trans, trans)-tpcb = tetrakis(4-pyridyl)cyclobutane). The tpcb ligands in the crystals of 1a show an intriguing in situ thermal isomerisation. The nanospheres of 1 can be obtained by recrystallization in DMSO/alcohol. The nanospheres of 1a can also be readily produced from the corresponding nanospheres of 1 by the photocyclodimerization method. Compared with those of 1a, the nanospheres of 1 display highly selective sensing of Fe(3+) ions over mixed metal ions through fluorescence quenching. Moreover, the nanospheres of 1a can rapidly adsorb CR (congo red), MB (methylene blue) or RhB (rhodamine B) over MO (methyl orange) from aqueous solutions. This work offers a new photoinduced post-synthetic method for the synthesis of multifunctional MOFs, which show luminescence sensing of Fe(3+) ions and dye adsorption properties.

  12. 1D coordination polymers formed by tetranuclear lead(II) building blocks with carboxylate ligands: In situ isomerization of itaconic acid

    SciTech Connect

    Rana, Abhinandan; Jana, Swapan Kumar; Datta, Sayanti; Butcher, Raymond J.; Zangrando, Ennio; Dalai, Sudipta

    2013-11-15

    The synthesis of two new lead(II) coordination polymers, [Pb{sub 2}(mpic){sub 4}(H{sub 2}O)]·0.5H{sub 2}O (1) and [Pb{sub 2}(phen){sub 2}(cit)(mes)]·2H{sub 2}O (2) has been reported, where mpic=3-methyl picolinate, phen=o-phenanthroline, H{sub 2}cit=citraconic acid, H{sub 2}mes mesaconic acid. X-ray single crystal diffraction analyses showed that the complexes comprise topologically different 1D polymeric chains stabilized by weak interactions and both containing tetranuclear Pb{sub 4} units connected by carboxylate groups. In compound 1 3-methylpicolinic acid is formed in situ from 3-methyl piconitrile, and mesaconate and citraconate anions were surprisingly formed from itaconic acid during the synthesis of 2. The photoluminescence and thermal properties of the complexes have been studied. - Graphical abstract: Two new topologically different 1D coordination polymers formed by Pb{sub 4} clusters have been synthesized and characterized by X-ray analysis. The luminescence and thermal properties have been studied. Display Omitted - Highlights: • Both the complexes, made up of different ligands, forms topologycally different 1D polymeric chains containing Pb{sub 4} clusters. • The final structures are stabilized by weak interactions (H-bond, π∙∙∙π stacking). • In complex 1, the 3-methylpicolinic acid is generated in situ from 3-methyl piconitrile. • Mesaconate and citraconate anions are surprisingly formed in situ from itaconic acid during the synthesis of complex 2, indicating an exceptional transformation.

  13. Can a highly flexible copper(i) cluster-containing 1D and 2D coordination polymers exhibit MOF-like properties?

    PubMed

    Bonnot, Antoine; Juvenal, Frank; Lapprand, Anthony; Fortin, Daniel; Knorr, Michael; Harvey, Pierre D

    2016-07-28

    The reaction of CuI with the highly flexible dithioether ligand p-TolS(CH2)8STol-p affords both in MeCN or in EtCN the 2D coordination polymers [Cu8I8{p-TolS(CH2)8STol-p}3(solvent)2]n (1·MeCN and 1·EtCN) containing octanuclear Cu8I8 clusters as connection nodes. In contrast, treatment of CuI with p-tBuC6H4S(CH2)8SC6H4But-p in EtCN solution leads to the formation of the luminescent 1D CP [Cu4I4{tBuC6H4S(CH2)8SC6H4-tBu}2(EtCN)2]n (2·EtCN) incorporating Cu4(μ3-I)4 clusters of the closed cubane type as secondary building units (SBUs). The 2D coordination polymers 1·MeCN and 1·EtCN demonstrate the ability to lose their solvent crystallisation molecules under vacuum and readsorb the same or a new one using vapor as monitored by powder X-ray diffraction, thermogravimetric, IR, chromaticity, emission spectra and emission lifetime measurements. Conversely, the 1D material 2·EtCN does not readsorb EtCN, likely due to the collapse of the macrocycles formed by the metal cluster nodes and flexible long-chained ArSC8SAr ligands but absorbs a smaller substrate such as CO2. PMID:27333826

  14. A Zn(II) coordination polymer and its photocycloaddition product: syntheses, structures, selective luminescence sensing of iron(III) ions and selective absorption of dyes.

    PubMed

    Hu, Fei-long; Shi, Yi-Xiang; Chen, Huan-Huan; Lang, Jian-Ping

    2015-11-21

    One coordination polymer [Zn2(L)2(bpe)2(H2O)2] (1) (L = 4,4'-((1,2-phenylenebis(methylene))bis(oxy))dibenzoic acid; bpe = (E)-1,2-di(pyridin-4-yl)ethene) was prepared and structurally determined. Compound 1 has a chain structure in which its pair of bpe ligands is arranged in a head-to-tail manner with their C=C bonds being close enough for a [2 + 2] cycloaddition reaction. Upon exposure to UV light, compound 1 undergoes a single-crystal-to-single-crystal (SCSC) [2 + 2] photodimerization to generate one 2D coordination polymer [Zn(L)(rctt-tpcb)0.5(H2O)] (1a) (rctt (regio cis, trans, trans)-tpcb = tetrakis(4-pyridyl)cyclobutane). The tpcb ligands in the crystals of 1a show an intriguing in situ thermal isomerisation. The nanospheres of 1 can be obtained by recrystallization in DMSO/alcohol. The nanospheres of 1a can also be readily produced from the corresponding nanospheres of 1 by the photocyclodimerization method. Compared with those of 1a, the nanospheres of 1 display highly selective sensing of Fe(3+) ions over mixed metal ions through fluorescence quenching. Moreover, the nanospheres of 1a can rapidly adsorb CR (congo red), MB (methylene blue) or RhB (rhodamine B) over MO (methyl orange) from aqueous solutions. This work offers a new photoinduced post-synthetic method for the synthesis of multifunctional MOFs, which show luminescence sensing of Fe(3+) ions and dye adsorption properties. PMID:26458568

  15. Nanoflakes of an aminoacid-based chiral coordination polymer: Synthesis, optical and electrochemical properties, and application in electrochemical sensing of H{sub 2}O{sub 2}

    SciTech Connect

    Zhou, Bo; Liang, Li-Mei; Yao, Jie

    2015-03-15

    Nanoflakes of an aminoacid-based chiral coordination polymer (CP), [Cu{sub 2}(tyr){sub 2}(bipy)]{sub n}, were synthesized successfully in the presence of surfactant, as evidenced by the XRD and SEM results. UV–vis absorption spectrometry and fluorescence spectrometry were used to investigate the optical properties of the CP, which was found to be mainly attributed to the ligands, while the forming of the CP caused only slight change. On the other hand, Cu(II) ions acted as electrocatalytic active sites of the CP, as evidenced by cyclic voltammetry. The CP also showed good performance in the electrochemical sensing of H{sub 2}O{sub 2}: sensitivity of 85.6 mA mol{sup −1} L cm{sup −2}, linear range of 1.0×10{sup −5}–7.69×10{sup −3} M, detection limit of 1.0×10{sup −5} M (S/N=3), and fast response in mere 5 s. - Graphical abstract: Nanoflakes of an aminoacid-based chiral coordination polymer (CP), [Cu{sub 2}(tyr){sub 2}(bipy)]{sub n}, were synthesized successfully and showed good performance in the electrochemical sensing of H{sub 2}O{sub 2}. - Highlights: • Synthesis of nanoflakes of an aminoacid-based chiral CP. • Optical and electrochemical properties resulting respectively from ligands and Cu{sup II}. • Good performance in enzyme-free electrochemical sensing of H{sub 2}O{sub 2}.

  16. The first quaternary lanthanide(III) nitride iodides: Na M4N 2I 7 ( M=La-Nd)

    NASA Astrophysics Data System (ADS)

    Schurz, Christian M.; Schleid, Thomas

    2010-10-01

    In attempts to synthesize lanthanide(III) nitride iodides with the formula M2NI 3 ( M=La-Nd), moisture-sensitive single crystals of the first quaternary sodium lanthanide(III) nitride iodides Na M4N 2I 7 (orthorhombic, Pna2 1; Z=4; a=1391-1401, b=1086-1094, c=1186-1211 pm) could be obtained. The dominating structural features are {[}∞1 chains of trans-edge linked [N M4] 9+ tetrahedra, which run parallel to the polar 2 1-axis [001]. Between the chains, direct bonding via special iodide anions generates cages, in which isolated [NaI 6] 5- octahedra are embedded. The IR spectrum of NaLa 4N 2I 7 recorded from 100 to 1000 cm -1 shows main bands at υ=337, 373 and 489 cm -1. With decreasing radii of the lanthanide trications these bands, which can be assigned as an influence of the vibrations of the condensed [N M4] 9+ tetrahedra, are shifted toward higher frequencies for the Na M4N 2I 7 series ( M=La-Nd), following the lanthanide contraction.

  17. Microwave assisted synthesis, spectroscopic, electrochemical and DNA cleavage studies of lanthanide(III) complexes with coumarin based imines.

    PubMed

    Kapoor, Puja; Fahmi, Nighat; Singh, R V

    2011-12-01

    The present work stems from our interest in the synthesis, characterization and biological evaluation of lanthanide(III) complexes of a class of coumarin based imines which have been prepared by the interaction of hydrated lanthanide(III) chloride with the sodium salts of 3-acetylcoumarin thiosemicarbazone (ACTSZH) and 3-acetylcoumarin semicarbazone (ACSZH) in 1:3 molar ratio using thermal as well as microwave method. Characterization of the ligands as well as the metal complexes have been carried out by elemental analysis, melting point determinations, molecular weight determinations, magnetic moment, molar conductance, IR, (1)H NMR, (13)C NMR, electronic, EPR, X-ray powder diffraction and mass spectral studies. Spectral studies confirm ligands to be monofunctional bidentate and octahedral environment around metal ions. The redox behavior of one of the synthesized metal complex was investigated by cyclic voltammetry. Further, free ligands and their metal complexes have been screened for their antimicrobial as well as DNA cleavage activity. The results of these findings have been presented and discussed.

  18. Microwave assisted synthesis, spectroscopic, electrochemical and DNA cleavage studies of lanthanide(III) complexes with coumarin based imines

    NASA Astrophysics Data System (ADS)

    Kapoor, Puja; Fahmi, Nighat; Singh, R. V.

    2011-12-01

    The present work stems from our interest in the synthesis, characterization and biological evaluation of lanthanide(III) complexes of a class of coumarin based imines which have been prepared by the interaction of hydrated lanthanide(III) chloride with the sodium salts of 3-acetylcoumarin thiosemicarbazone (ACTSZH) and 3-acetylcoumarin semicarbazone (ACSZH) in 1:3 molar ratio using thermal as well as microwave method. Characterization of the ligands as well as the metal complexes have been carried out by elemental analysis, melting point determinations, molecular weight determinations, magnetic moment, molar conductance, IR, 1H NMR, 13C NMR, electronic, EPR, X-ray powder diffraction and mass spectral studies. Spectral studies confirm ligands to be monofunctional bidentate and octahedral environment around metal ions. The redox behavior of one of the synthesized metal complex was investigated by cyclic voltammetry. Further, free ligands and their metal complexes have been screened for their antimicrobial as well as DNA cleavage activity. The results of these findings have been presented and discussed.

  19. Self-assembly of iron coordination polymer of bowl-shaped N-ligand and dodecamolybdosilicate anion

    NASA Astrophysics Data System (ADS)

    Tang, Qun; Chen, Ya-Guang

    2014-06-01

    [FeII2(ttmb)2(H2O)6][SiMo12O40]·4H2O (1) (ttmb = 1,3,5-tris(triazol-1-ylmethyl) benzene) was synthesized under hydrothermal conditions and characterized by IR spectroscopy, TG analysis and X-ray diffraction method. In 1 the bowl-like tridentate ligand, ttmb, bridges Fe2+ ions forming a coordination polymeric layer, [FeII2(ttmb)2(H2O)6]n4n+, with a large dimensional grid of 7.00 × 7.11 Å, in the presence of Keggin-type polyoxoanion as a template. The coordination polymeric layers and the polyoxoanions are fused into an inorganic-organic hybrid by hydrogen bonds. The photoluminescent spectrum of 1 in solid state at room temperature shows that the coordination of ttmb to Fe2+ ion results in a quench of the ttmb intramolecular fluorescence and a weak O-Mo LMCT fluorescent emission was observed at 520 nm.

  20. Syntheses and structural characterization of mercury (II) coordination polymers with neutral bidentate flexible pyrazole-based ligands

    NASA Astrophysics Data System (ADS)

    Lalegani, Arash; Khaledi Sardashti, Mohammad; Salavati, Hossein; Asadi, Amin; Gajda, Roman; Woźniak, Krzysztof

    2016-03-01

    Mercury(II) coordination compounds [Hg(μ-bbd)(μ-SCN)4]n(1) and [Hg(bpp)(SCN)2] (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp), NCS- ligand and appropriate mercury(II) salts. Compound 1 forms a polymeric network with moieties which are connected by SCN groups and the mercury ions present as HgN3S2 trigonal bipyramides. The crystal structure of 2 is build of monomers and the mercury(II) ion adopts an HgN2S2 tetrahedral geometry. In the complex 1, each bbd acts as bridging ligand connecting Hg(μ-SCN)4 ions, while in the complex 2, the bpp ligand is coordinated to an mercury(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Moreover, in the tetrahedral structure of 2, the neutral molecules form a 1D chain structure through the C-H···N hydrogen bonds, whereas in 1 no hydrogen bonds are observed. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction.