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Sample records for 2d coordination polymer

  1. Hysteretic Spin Crossover in Two-Dimensional (2D) Hofmann-Type Coordination Polymers.

    PubMed

    Liu, Wei; Wang, Lu; Su, Yu-Jun; Chen, Yan-Cong; Tucek, Jiri; Zboril, Radek; Ni, Zhao-Ping; Tong, Ming-Liang

    2015-09-08

    Three new two-dimensional (2D) Hofmann-type coordination polymers with general formula [Fe(3-NH2py)2M(CN)4] (3-NH2py = 3-aminopyridine, M = Ni (1), Pd (2), Pt (3)) have been synthesized. Magnetic susceptibility measurements show that they exhibited cooperative spin crossover (SCO) with remarkable hysteretic behaviors. Their hysteresis widths are 25, 37, and 30 K for 1-3, respectively. The single-crystal structure of 1 suggest that the pseudo-octahedral Fe sites are equatorially bridged by [M(CN)4](2-) to form 2D grids and axially coordinated by 3-NH2py ligands. The intermolecular interactions between layers (the offset face-to-face π···π interactions, hydrogen bonds, and weak N(amino)···Ni(II) contacts) together with the covalent bonds bridged by [M(CN)4](2-) units are responsible to the significant cooperativity.

  2. A novel coordination polymer containing both interdigitated 1D chains and interpenetrated 2D grids.

    PubMed

    Ayyappan, Ponnaiyan; Evans, Owen R; Lin, Wenbin

    2002-07-01

    A hydro(solvo)thermal reaction between zinc perchlorate and ethyl ester of a new pyridinecarboxylate bridging ligand of approximately 17.6 A in length yields a unique coordination polymer which contains both interdigitated infinite 1D chains and interpenetrated 2D rhombohedral grids [Zn(2.5)(L)(4)(mu(3)-OH)] x (H(2)O)(5), 1, where L is 3-[[4-(4-pyridylethenyl)phenyl]ethenyl]benzoate. The 1D chains contain mu(3)-bridged hydroxy groups and have a [Zn(4)(mu(3)-OH)(2)(L)(6)] stoichiometry, while the 2D grids have a Zn(L)(2) formula and diagonal distances of 31.7 and 25.2 A. Crystal data for 1: monoclinic space group P2/c, a = 15.686(2) A, b = 12.6103(16) A, c = 38.999(5) A, beta = 98.397(2) degrees, and Z = 4.

  3. 2D coordination polymers of macrocyclic oxamide with polycarboxylates: syntheses, crystal structures and magnetic properties.

    PubMed

    Sun, Ya-Qiu; Xu, Yan-Yan; Gao, Dong-Zhao; Zhang, Guo-Ying; Liu, Yiao-Xu; Wang, Jing; Liao, Dai-Zheng

    2012-05-14

    Five new 2D coordination polymers, [Co(nip)(CuL)(H(2)O)]·CH(3)OH (1), [Mn(ip)(NiL)]·0.63H(2)O (2), [Cu(ip)(CuL)] (3), [Mn(6)(CuL)(6)(btc)(4)(H(2)O)(4)]·7H(2)O (4), and [Cu(CuL)(Hbtc)(H(2)O)] (5)(ML, H(2)L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-diene; H(2)nip = 5-nitroisophthalic acid; H(2)ip = m-isophthalic acid; H(3)btc = 1,3,5-benzenetricarboxylic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1-5 exhibit different 2D layered structures formed by Co(2)Cu(2) (1), Mn(2)Ni(2) (2), Cu(4) (3), Mn(3)Ni(3) (4), Cu(4) (5) units, respectively, via the oxamide and diverse carboxylic acid bridges. Compounds 1, 2, 3 and 5 are uninodal 4-connected (4, 4)-grids topology, while complex 4 possesses a 2D network with (3, 4)-connected (4(2).8)(4)(4(3).6(2).8)(3) topology. The results of magnetic determination show pronounced antiferromagnetic interactions in 1-4.

  4. Assembly of 3D coordination polymers from 2D sheets by [2+2] cycloaddition reaction.

    PubMed

    Medishetty, Raghavender; Tandiana, Rika; Koh, Lip Lin; Vittal, Jagadese J

    2014-01-27

    The synthesis of three 2D interdigitated Zn(II) coordination polymers (CPs), by using three monotopic ligands containing C=C bonds, is reported. Among these, two CPs with 4spy (4-styryl pyridine) and 2F-4spy (a 2'-fluoro derivative of 4spy) ligands showed quantitative formation of cyclobutane rings, thus demonstrating a unique synthetic procedure to synthesize metal-organic frameworks (MOFs) by using this photochemical reaction. Interestingly, these compounds can also be synthesized by mechanochemical grinding procedures by using Zn(OAc)2. In contrast, Zn(NO3)2 did not yield the required product, unlike in the solution route. In addition, compounds with 4vpy (4-vinylpyridine), 4spy and 2F-4spy ligands created different units in the CPs; 4vpy and 2F-4spy furnished paddle wheel units, whereas 4spy yielded tetrahedral Zn(II) repeating units. Furthermore, the change in coordination geometry manifests in the photoluminescence properties, attributed to the difference in charge-transfer and ligand-centered fluorescent phenomenon.

  5. 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

    2016-05-04

    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.

  6. Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol.

    PubMed

    Troyano, Javier; Perles, Josefina; Amo-Ochoa, Pilar; Martínez, Jose Ignacio; Concepción Gimeno, Maria; Fernández-Moreira, Vanesa; Zamora, Félix; Delgado, Salomé

    2016-12-12

    Solvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3 X(HT)2 ]n (X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu-S, Cu-X and Cu-Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ3 -bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4 -mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materials.

  7. Structures and Luminescent Properties of Two 2D Coordination Polymers Containing Tb(III) or Dy(III) Ions.

    PubMed

    An, Xiaoping; Wang, Hongsheng; Li, Gongchun

    2014-03-01

    Two 2D rare earth terbium and dysprosium coordination polymers with 2,4-pyridinedicarboxylate and oxalate anions have been synthesized by hydrothermal method, the formula is {[RE(pda)(ox)0.5(H2O)4]·2H2O}n (RE = Tb (1) and Dy (2); H2pda = 2,4-pyridinedicarboxylic acid; ox = oxalate anion). The two complexes are isomorphic and crystallized in monoclinic system, P21/c space group. Each pda anion connects two rare earth ions with 2- carboxyl group and the nitrogen atom but the 4- carboxyl group does not coordinate with rare earth ions. Each ox anion connects two rare earth ions by μ 2-bridge way. Both the complexes exhibit intense characteristic luminescence of Tb(III) or Dy(III) ion with excitation of UV-rays.

  8. 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.

  9. Synthesis and structural characterization of homochiral 2D coordination polymers of zinc and copper with conformationally flexible ditopic imidazolium-based dicarboxylate ligands.

    PubMed

    Nicasio, Antonio I; Montilla, Francisco; Álvarez, Eleuterio; Colodrero, Rosario P; Galindo, Agustín

    2017-01-03

    Different novel coordination polymers containing zinc, 1-4, and copper, 5-8, metals, connected via chiral imidazolium-based dicarboxylate ligands, [L(R)](-), were isolated by reaction between zinc acetate or copper acetate and enantiomerically pure HL(R) compounds. They were characterised and structurally identified by X-ray diffraction methods (single crystal and powder). These compounds are two-dimensional homochiral coordination polymers, [M(L(R))2]n, in which the metal ions are coordinated by the two carboxylate groups of [L(R)](-) anions in a general bridging monodentate μ(2)-κ(1)-O(1),κ(1)-O(3) fashion that afforded tetrahedral metal coordination environments for zinc, 1-4, and square planar for copper, 5-8, complexes. In all the compounds the 3D supramolecular architecture is constructed by non-covalent interactions between the hydrophobic parts (R groups) of the homochiral 2D coordination polymers and, in some cases, by weak C-HO non-classical hydrogen bonds that provided, in general, a dense crystal packing. DFT calculations on the [L(R)](-) anions confirmed their conformational flexibility as ditopic linkers and this fact makes possible the formation of different coordination polymers for four-coordinated metal centers. Preliminary studies on the Zn-catalyzed synthesis of chiral α-aminophosphonates were carried out and, unfortunately, no enantioselectivity was observed in these reactions.

  10. 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.

  11. Two 2D Cd(II) coordination polymers based on asymmetrical Schiff-base ligand: synthesis, crystal structures and luminescent properties.

    PubMed

    Dang, Dong-Bin; Li, Meng-Meng; Bai, Yan; Zhou, Rui-Min

    2013-02-15

    Two new two-dimensional coordination polymers [Cd(3)L(2)(SCN)(6)](n) (1) and [CdLI(2)](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 N(triazolyl) 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 C-H···π and π-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 C-H···π and π-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.

  12. Synthesis and characterization of three 2D Cd (II) coordination polymers built with terphenyl-2, 2‧, 4, 4‧-tetracarboxylate and flexible bis(imidazole)

    NASA Astrophysics Data System (ADS)

    Wang, Ji-Jiang; Tang, Long; Zhang, Mei-Li; Gao, Lou-Jun; Ren, Yi-Xia; Hou, Xiang-Yang; Fu, Feng

    2015-04-01

    Three new CdII coordination polymers, namely, {[Cd2 (L) (1, 2-bix)2(H2O)2]ṡ2H2O}n(1), [Cd2 (L) (1, 3-bix)2]n (2), and {[Cd (H2L) (1, 4-bix) (H2O)2]ṡ2H2O}n (3) [H4L = terphenyl-2, 2‧, 4, 4‧-tetracarboxylic acid, 1, n-bix = 1, n-bis(imidazol-l-ylmethyl) benzene (n = 2, 3, 4)], have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR, thermogravimetric analysis, and fluorescent analysis. Complex 1 is a 2D wavelike network structure incorporating the dinuclear Cd2 (1, 2-bix)2 units, whereas complex 2 possesses a 2D stair-like network structure consisting of the dinuclear Cd2O2 units. Complex 3 features a 2D puckered network constructed by 1D [Cd (H2L)]n and 1D [Cd (1, 4-bix)]n chains. The results show that the structural diversity of the polymers is mainly attributed to the usage of diverse ancillary bis (imidazol-1-ylmethyl)-benzene isomers ligands. The thermal stabilities and photoluminescence behaviors were also investigated.

  13. 2D l-Di-toluoyl-tartaric acid Lanthanide Coordination Polymers: Toward Single-component White-Light and NIR Luminescent Materials.

    PubMed

    Niu, Wan-Ying; Sun, Jing-Wen; Yan, Peng-Fei; Li, Yu-Xin; An, Guang-Hui; Li, Guang-Ming

    2016-02-18

    A series of five l-di-p-toluoyl-tartaric acid (l-DTTA) lanthanide coordination polymers, namely {[Ln4 K(4)  L6 (H2O)x ]⋅yH2 O}n , [Ln=Dy (1), x=24, y=12; Ln=Ho (2), x=23, y=12; Ln=Er (3), x=24, y=12; Ln=Yb (4), x=24, y=11; Ln=Lu (5), x=24, y=12] have been isolated by simple reactions of H2L (H2 L= L-DTTA) with LnCl3 ⋅6 H2O at ambient temperature. X-ray crystallographic analysis reveals that complexes 1-5 feature two-dimensional (2D) network structures in which the Ln(3+) ions are bridged by carboxylate groups of ligands in two unique coordinated modes. Luminescent spectra demonstrate that complex 1 realizes single-component white-light emission, while complexes 2-4 exhibit a characteristic near-infrared (NIR) luminescence in the solid state at room temperature.

  14. Self-assembly of silver(I) coordination polymers from aminopyrimidyl derivatives and malonate acid: From 1D chain to 2D layer

    NASA Astrophysics Data System (ADS)

    Sun, Di; Zhang, Na; Xu, Qin-Juan; Luo, Geng-Geng; Huang, Rong-Bin; Zheng, Lan-Sun

    2010-04-01

    Two new silver(I) coordination polymers (CPs) of the formula [Ag 2(dmapym) 4(mal)·H 2O] n ( 1) and [Ag 3(apym) 3(mal)NO 3] n ( 2) (dmapym = 2-amino-4,6-dimethylprimidine, apym = 2-aminopyrimidine, H 2mal = malonate) have been synthesized by reactions of AgNO 3 and 2-aminopyrimidyl ligands with malonate under the ammoniacal condition. Both complexes have been characterized by element analysis, IR and single-crystal X-ray diffraction. The monodentate dmapym and tridentate mal ligands link Ag(I) ions to give complex 1 a one-dimensional (1D) H-shaped chain structure. The complex 2 is a two-dimensional (2D) double sheet structure constructed by (4, 4) single sheet. Additionally, the hydrogen-bonding and C-H⋯π interactions also direct the self-assembly of supramolecular architectures. The photoluminescence properties of the 1 and 2 were investigated in the solid state at room temperature.

  15. 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.

  16. Hybrid materials based on novel 2D lanthanide coordination polymers covalently bonded to amine-modified SBA-15 and MCM-41: assembly, characterization, structural features, thermal and luminescence properties.

    PubMed

    Wang, Jun; Dou, Wei; Kirillov, Alexander M; Liu, Weisheng; Xu, Cailing; Fang, Ran; Yang, Lizi

    2016-11-22

    Three novel 2D coordination polymers [Tb2(μ4-L)2(μ-HL)(μ-HCOO)(DEF)]n (Tb-L), [Eu(μ4-L)(L)(H2O)2]n (Eu-L), and [Nd(μ4-L)(L)(H2O)2]n (Nd-L) were assembled from the corresponding lanthanide(iii) nitrates and 5 methoxy-(4-benzaldehyde)-1,3-benzenedicarboxylic acid (H2L) as a main multifunctional building block bearing carboxylate and aldehyde functional groups, using H2O/DEF {DEF = N,N-diethylformamide} as a reaction medium. The obtained coordination polymers were isolated as stable microcrystalline solids and fully characterized by elemental analysis, FT-IR spectroscopy, TGA, BET, PXRD, and single-crystal X-ray diffraction methods. Their structures feature intricate 2D metal-organic networks, which were topologically classified as underlying layers with the 4,6L26 (for Tb-L) or sql (for Eu-L and Nd-L) topologies. Besides, a novel series of mesoporous hybrid materials wherein the Tb-L, Eu-L, or Nd-L coordination polymers are covalently grafted into the amine-functionalized SBA-15-NH2 or MCM-41-NH2 matrices (via the formation of Schiff-base groups) was also synthesized and fully characterized. These hybrid materials show high thermal and photoluminescence stability, as well as remarkable chemical resistance to boiling water, and acidic or alkaline medium. Luminescent properties of the parent coordination polymers and derived hybrid materials are investigated in detail, showing that the latter combine the luminescent characteristics (intense green or red emissions and excellent stability) of lanthanide coordination polymers and structural features of ordered mesoporous silica molecular sieves. Moreover, light emitting devices were assembled, by coating the hybrid materials onto the surface of UV-LED bulbs, and showed excellent light emitting properties.

  17. Self-Construction from 2D to 3D: One-Pot Layer-by-Layer Assembly of Graphene Oxide Sheets Held Together by Coordination Polymers.

    PubMed

    Zakaria, Mohamed B; Li, Cuiling; Ji, Qingmin; Jiang, Bo; Tominaka, Satoshi; Ide, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko; Yamauchi, Yusuke

    2016-07-11

    Deposition of Ni-based cyanide bridged coordination polymer (NiCNNi) flakes onto the surfaces of graphene oxide (GO) sheets, which allows precise control of the resulting lamellar nanoarchitecture by in situ crystallization, is reported. GO sheets are utilized as nucleation sites that promote the optimized crystal growth of NiCNNi flakes. The NiCNNi-coated GO sheets then self-assemble and are stabilized as ordered lamellar nanomaterials. Regulated thermal treatment under nitrogen results in a Ni3 C-GO composite with a similar morphology to the starting material, and the Ni3 C-GO composite exhibits outstanding electrocatalytic activity and excellent durability for the oxygen reduction reaction.

  18. New coordination polymers from 1D chain, 2D layer to 3D framework constructed from 1,2-phenylenediacetic acid and 1,3-bis(4-pyridyl)propane flexible ligands

    SciTech Connect

    Xin Lingyun; Liu Guangzhen; Wang Liya

    2011-06-15

    The hydrothermal reactions of Cd, Zn, or Cu(II) acetate salts with H{sub 2}PHDA and BPP flexible ligands afford three new coordination polymers, including [Cd(PHDA)(BPP)(H{sub 2}O)]{sub n}(1), [Zn(PHDA)(BPP)]{sub n}(2), and [Cu{sub 2}(PHDA){sub 2}(BPP)]{sub n}(3) (H{sub 2}PHDA=1,2-phenylenediacetic acid, BPP=1,3-bis(4-pyridyl)propane). The single-crystal X-ray diffractions reveal that all three complexes feature various metal carboxylate subunits extended further by the BPP ligands to form a diverse range of structures, displaying a remarked structural sensitivity to metal(II) cation. Complex 1 containing PHDA-bridged binuclear cadmium generates 1D double-stranded chain, complex 2 results in 2D{yields}2D interpenetrated (4,4) grids, and complex 3 displays a 3D self-penetrated framework with 4{sup 8}6{sup 6}8 rob topology. In addition, fluorescent analyses show that both 1 and 2 exhibit intense blue-violet photoluminescence in the solid state. - Graphical Abstract: We show diverse supramolecular frameworks based on the same ligands (PHDA and BPP) and different metal acetate salts including 1D double-stranded chain, 2D {yields} 2D twofold interpenetrated layer, and 3D self-penetration networks. Highlights: > Three metal(II = 2 /* ROMAN ) coordination polymers were synthesized using H{sub 2}PHDA and BPP. > The diversity of structures show a remarked sensitivity to metal(II) center. > Complexes show the enhancement of fluorescence compared to that of free ligand.

  19. Assembly of 1D, 2D and 3D lanthanum(iii) coordination polymers with perchlorinated benzenedicarboxylates: positional isomeric effect, structural transformation and ring-opening polymerisation of glycolide.

    PubMed

    Chen, Sheng-Chun; Dai, An-Qi; Huang, Kun-Lin; Zhang, Zhi-Hui; Cui, Ai-Jun; He, Ming-Yang; Chen, Qun

    2016-02-28

    Utilizing a series of positional isomers of tetrachlorinated benzenedicarboxylic acid ligands, seven La(iii)-based coordination polymers were solvothermally synthesized and structurally characterized. Their structural dimensionalities varying from 1D double chains, to the 2D 3,4,5-connected network, to 3D 6-connected pcu topological nets are only governed by the positions of carboxyl groups on the tetrachlorinated benzene ring. A comprehensive analysis and comparison reveals that the size of the carbonyl solvent molecules (DMF, DEF, DMA, and NMP) can affect the coordination geometries around the La(iii) ions, the coordination modes of carboxylate groups, the packing arrangements, and the void volumes of the overall crystal lattices. One as-synthesized framework further shows an unprecedented structural transformation from a 3D 6-connected network to a 3D 4,5-connected net through the dissolution and reformation pathway in water, suggesting that these easily hydrolyzed lanthanide complexes may serve as precursors to produce new high-dimensional frameworks. The bulk solvent-free melt polymerisation of glycolide utilizing these La(iii) complexes as initiators has been reported herein for the first time. All complexes were found to promote the polymerization of glycolide over a temperature range of 200 to 220 °C, producing poly(glycolic acid) (PGA) with a molecular weight up to 93,280. Under the same experimental conditions, the different catalytic activities for these complexes may result from their structural discrepancy.

  20. Hydrothermal synthesis of zinc(II)-phosphonate coordination polymers with different dimensionality (0D, 2D, 3D) and dimensionality change in the solid phase (0D→3D) induced by temperature

    SciTech Connect

    Fernández-Zapico, Eva; Montejo-Bernardo, Jose; Fernández-González, Alfonso; García, José R. García-Granda, Santiago

    2015-05-15

    Three new zinc(II) coordination polymers, [Zn(HO{sub 3}PCH{sub 2}CH{sub 2}COO)(C{sub 12}H{sub 8}N{sub 2})(H{sub 2}O)] (1), [Zn{sub 3}(O{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(C{sub 12}H{sub 8}N{sub 2})](H{sub 2}O){sub 3.40} (2) and [Zn{sub 5}(HO{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(O{sub 3}PCH{sub 2}CH{sub 2}COO){sub 2}(C{sub 12}H{sub 8}N{sub 2}){sub 4}](H{sub 2}O){sub 0.32} (3), with different structural dimensionality (0D, 2D and 3D, respectively) have been prepared by hydrothermal synthesis, and their structures were determined by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system (P2{sub 1}/c) forming discrete dimeric units bonded through H-bonds, while compounds 2 and 3 crystallize in the triclinic (P−1) and the monoclinic (C2/c) systems, respectively. Compound 3, showing three different coordination numbers (4, 5 and 6) for the zinc atoms, has also been obtained by thermal treatment of 1 (probed by high-temperature XRPD experiments). The crystalline features of these compounds, related to the coordination environments for the zinc atoms in each structure, provoke the increase of the relative fluorescence for 2 and 3, compared to the free phenanthroline. Thermal analysis (TG and DSC) and XPS studies have been also carried out for all compounds. - Graphical abstract: Three new coordination compounds of zinc with 2-carboxyethylphosphonic acid (H{sub 2}PPA) and phenanthroline have been obtained by hydrothermal synthesis. The crystalline structure depends on the different coordination environments of the zinc atoms (see two comparative Zn{sub 6}-moieties). The influence of the different coordination modes of H{sub 2}PPA with the central atom in all structures have been studied, being found new coordination modes for this ligand. Several compounds show a significant increase in relative fluorescence with respect to the free phenanthroline. - Highlights: • Compounds have been obtained modifying the reaction time and the rate of

  1. 2D water layer enclathrated between Mn(II)-Ni(CN){sub 4} coordination frameworks

    SciTech Connect

    Ray, Ambarish; Bhowmick, Indrani; Sheldrick, William S.; Jana, Atish Dipankar; Ali, Mahammed

    2009-10-15

    A [Ni(CN){sub 4}]{sup 2-}based two-dimensional Mn(II) coordination polymer {l_brace}Mn(H{sub 2}O){sub 2}[NiCN]{sub 4}.4H{sub 2}O{r_brace}, in which the coordination layers are stacked on top of each other sandwiching 2D water layer of boat-shaped hexagonal water clusters has been synthesized. The complex exhibits high thermal decomposition temperature and reversible water absorption, which were clearly demonstrated by thermal and PXRD studies on the parent and rehydrated complex after dehydration. - Abstract: A coordination polymer, {l_brace}Mn(H{sub 2}O){sub 2}[NiCN]{sub 4}.4H{sub 2}O{r_brace}{sub n}, showed that the coordination layers are stacked on top of each other sandwiching 2D ice layer of boat-shaped hexagonal water clusters . Display Omitted

  2. Synthesis, X-ray crystal structure, optical properties and DFT studies of a new 2D layered iodide bridged Pb(II) coordination polymer with 2,3-bis(2-pyridyl)pyrazine

    SciTech Connect

    Saghatforoush, Lotfali Bakhtiari, Akbar; Gheleji, Hojjat

    2015-01-15

    The synthesis of two dimensional (2D) coordination polymer [Pb{sub 2}(µ-I){sub 2}(µ-dpp-N,N,N,N)(µ-dpp-N,N)I{sub 2}]{sub n} (dpp=2,3-bis(2-pyridyl)pyrazine) is reported. As determined by X-ray diffraction of a twinned crystal, the dpp ligand simultaneously adopts a bis–bidentate and bis–monodentate coordination mode in the crystal structure of compound. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that the compound is an indirect band gap semiconductor. According to the DFT calculations, the observed emission of the compound at 600 nm in solid phase could be attributed to arise from an excited LLCT state (dpp-π{sup ⁎} [C-2p and N-2p states, CBs] to I-6p state [VBs]). The linear optical properties of the compound are also calculated by DFT method. The structure of the compound in solution phase is discussed based on the measured {sup 1}H NMR and fluorescence spectra in DMSO. TGA studies indicate that the compound is thermally stable up to 210 °C. - Graphical abstract: The synthesis, crystal structure and emission spectra of [Pb{sub 2}(µ-I){sub 2}(µ-dpp-N,N,N,N)(µ-dpp-N,N)I{sub 2}]{sub n} is presented. The electronic band structure and linear optical properties of the compound are calculated by the DFT method. - Highlights: • Two dimensional [Pb{sub 2}(µ-I){sub 2}(µ-dpp-N,N,N,N)(µ-dpp-N,N)I{sub 2}]{sub n} has been prepared. • The structure of the compound is determined by XRD of a twinned crystal. • DFT calculations indicate that the compound is an indirect band gap semiconductor. • As shown by DFT calculations, the emission band of the compound is LLCT. • Solution phase structure of compound is explored by {sup 1}H NMR and emission spectra.

  3. Band-structure engineering in conjugated 2D polymers.

    PubMed

    Gutzler, Rico

    2016-10-26

    Conjugated polymers find widespread application in (opto)electronic devices, sensing, and as catalysts. Their common one-dimensional structure can be extended into the second dimension to create conjugated planar sheets of covalently linked molecules. Extending π-conjugation into the second dimension unlocks a new class of semiconductive polymers which as a consequence of their unique electronic properties can find usability in numerous applications. In this article the theoretical band structures of a set of conjugated 2D polymers are compared and information on the important characteristics band gap and valence/conduction band dispersion is extracted. The great variance in these characteristics within the investigated set suggests 2D polymers as exciting materials in which band-structure engineering can be used to tailor sheet-like organic materials with desired electronic properties.

  4. Commensurate Superstructure of the {Cu(NO3)(H2O)}(HTae)(Bpy) Coordination Polymer: An Example of 2D Hydrogen-Bonding Networks as Magnetic Exchange Pathway.

    PubMed

    Fernández de Luis, Roberto; Larrea, Edurne S; Orive, Joseba; Lezama, Luis; Arriortua, María I

    2016-11-21

    The average and commensurate superstructures of the one-dimensional coordination polymer {Cu(NO3)(H2O)}(HTae)(Bpy) (H2Tae = 1,1,2,2-tetraacetylethane, Bpy = 4,4'-bipyridine) were determined by single-crystal X-ray diffraction, and the possible symmetry relations between the space group of the average structure and the superstructure were checked. The crystal structure consists in parallel and oblique {Cu(HTae)(Bpy)} zigzag metal-organic chains stacked along the [100] crystallographic direction. The origin of the fivefold c axis in the commensurate superstructure is ascribed to a commensurate modulation of the coordination environment of the copper atoms. The commensurately ordered nitrate groups and coordinated water molecules establish a two-dimensional hydrogen-bonding network. Moreover, the crystal structure shows a commensurate to incommensurate transition at room temperature. The release of the coordination water molecules destabilizes the crystal framework, and the compound shows an irreversible structure transformation above 100 °C. Despite the loss of crystallinity, the spectroscopic studies indicate that the main building blocks of the crystal framework are retained after the transformation. The hydrogen-bonding network not only plays a crucial role stabilizing the crystal structure but also is an important pathway for magnetic exchange transmission. In fact, the magnetic susceptibility curves indicate that after the loss of coordinated water molecules, and hence the collapse of the hydrogen-bonding network, the weak anti-ferromagnetic coupling observed in the initial compound is broken. The electron paramagnetic resonance spectra are the consequence of the average signals from Cu(II) with different orientations, indicating that the magnetic coupling is effective between them. In fact, X- and Q-band data are reflecting different situations; the X-band spectra show the characteristics of an exchange g-tensor, while the Q-band signals are coming from both

  5. Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6'-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer.

    PubMed

    Seredyuk, Maksym; Piñeiro-López, Lucía; Muñoz, M Carmen; Martínez-Casado, Francisco J; Molnár, Gábor; Rodriguez-Velamazán, José Alberto; Bousseksou, Azzedine; Real, José Antonio

    2015-08-03

    Deprotonation of the ionogenic tetradentate ligand 6,6'-bis(1H-tetrazol-5-yl)-2,2'-bipyridine [H2bipy(ttr)2] in the presence of Fe(II) in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)2][Hbipy(ttr)2]}·3MeOH (1) and {Fe[bipy(ttr)2]}n (2). The anions [Hbipy(ttr)2](-) and [bipy(ttr)2](2-) embrace the Fe(II) centers defining discrete molecular units 1 with the Fe(II) ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the Fe(II) is high-spin, and its Mössbauer spectrum is characterized by a relatively large average quadrupole splitting, ΔEQ = 3.42 mm s(-1). Compound 2 defines a strongly distorted octahedral environment for Fe(II) in which one [bipy(ttr)2](-) anion coordinates the equatorial positions of the Fe(II) center, while the axial positions are occupied by peripheral N-tetrazole atoms of two adjacent {Fe[bipy(ttr)2]}(0) moieties thereby generating an infinite double-layer sheet. Compound 2 undergoes an almost complete spin crossover transition between the high-spin and low-spin states centered at about 221 K characterized by an average variation of enthalpy and entropy ΔH(av) = 8.27 kJ mol(-1), ΔS(av) = 37.5 J K(-1) mol(-1), obtained from calorimetric DSC measurements. Photomagnetic measurements of 2 at 10 K show an almost complete light-induced spin state trapping (LIESST) effect which denotes occurrence of antiferromagnetic coupling between the excited high-spin species and TLIESST = 52 K. The crystal structure of 2 has been investigated in detail at various temperatures and discussed.

  6. 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.

  7. Porphyrin coordination polymer nanospheres and nanorods

    SciTech Connect

    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.

  8. A design principle of polymers processable into 2D homeotropic order

    PubMed Central

    Chen, Zhen; Chan, Yi-Tsu; Miyajima, Daigo; Kajitani, Takashi; Kosaka, Atsuko; Fukushima, Takanori; Lobez, Jose M.; Aida, Takuzo

    2016-01-01

    How to orient polymers homeotropically in thin films has been a long-standing issue in polymer science because polymers intrinsically prefer to lie down. Here we provide a design principle for polymers that are processable into a 2D homeotropic order. The key to this achievement was a recognition that cylindrical polymers can be designed to possess oppositely directed local dipoles in their cross-section, which possibly force polymers to tightly connect bilaterally, affording a 2D rectangular assembly. With a physical assistance of the surface grooves on Teflon sheets that sandwich polymer samples, homeotropic ordering is likely nucleated and gradually propagates upon hot-pressing towards the interior of the film. Consequently, the 2D rectangular lattice is constructed such that its b axis (side chains) aligns along the surface grooves, while its c axis (polymer backbone) aligns homeotropically on a Teflon sheet. This finding paves the way to molecularly engineered 2D polymers with anomalous functions. PMID:27897189

  9. A design principle of polymers processable into 2D homeotropic order

    NASA Astrophysics Data System (ADS)

    Chen, Zhen; Chan, Yi-Tsu; Miyajima, Daigo; Kajitani, Takashi; Kosaka, Atsuko; Fukushima, Takanori; Lobez, Jose M.; Aida, Takuzo

    2016-11-01

    How to orient polymers homeotropically in thin films has been a long-standing issue in polymer science because polymers intrinsically prefer to lie down. Here we provide a design principle for polymers that are processable into a 2D homeotropic order. The key to this achievement was a recognition that cylindrical polymers can be designed to possess oppositely directed local dipoles in their cross-section, which possibly force polymers to tightly connect bilaterally, affording a 2D rectangular assembly. With a physical assistance of the surface grooves on Teflon sheets that sandwich polymer samples, homeotropic ordering is likely nucleated and gradually propagates upon hot-pressing towards the interior of the film. Consequently, the 2D rectangular lattice is constructed such that its b axis (side chains) aligns along the surface grooves, while its c axis (polymer backbone) aligns homeotropically on a Teflon sheet. This finding paves the way to molecularly engineered 2D polymers with anomalous functions.

  10. Compatible, energy and symmetry preserving 2D Lagrangian hydrodynamics in rz-cylindrical coordinates

    SciTech Connect

    Shashkov, Mikhail; Wendroff, Burton; Burton, Donald; Barlow, A; Hongbin, Guo

    2009-01-01

    We present a new discretization for 2D Lagrangian hydrodynamics in rz geometry (cylindrical coordinates) that is compatible, energy conserving and symmetry preserving. We describe discretization of the basic Lagrangian hydrodynamics equations.

  11. 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.

  12. Infinite Coordination Polymer Nano- and Micro-Particles

    DTIC Science & Technology

    2015-06-12

    SECURITY CLASSIFICATION OF: Infinite coordination polymer (ICP) particles and metal- organic frameworks (MOFs) are attractive materials for a diverse...Coordination Polymer Nano- and Micro- Particles Report Title Infinite coordination polymer (ICP) particles and metal- organic frameworks (MOFs) are...Abstract Infinite coordination polymer (ICP) particles and metal- organic frameworks (MOFs) are attractive materials for a diverse array of

  13. Building a symbolic computer algebra toolbox to compute 2D Fourier transforms in polar coordinates.

    PubMed

    Dovlo, Edem; Baddour, Natalie

    2015-01-01

    The development of a symbolic computer algebra toolbox for the computation of two dimensional (2D) Fourier transforms in polar coordinates is presented. Multidimensional Fourier transforms are widely used in image processing, tomographic reconstructions and in fact any application that requires a multidimensional convolution. By examining a function in the frequency domain, additional information and insights may be obtained. The advantages of our method include: •The implementation of the 2D Fourier transform in polar coordinates within the toolbox via the combination of two significantly simpler transforms.•The modular approach along with the idea of lookup tables implemented help avoid the issue of indeterminate results which may occur when attempting to directly evaluate the transform.•The concept also helps prevent unnecessary computation of already known transforms thereby saving memory and processing time.

  14. 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.

  15. 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.

  16. Self-surface charge exfoliation and electrostatically coordinated 2D hetero-layered hybrids

    PubMed Central

    Yang, Min-Quan; Xu, Yi-Jun; Lu, Wanheng; Zeng, Kaiyang; Zhu, Hai; Xu, Qing-Hua; Ho, Ghim Wei

    2017-01-01

    At present, the technological groundwork of atomically thin two-dimensional (2D) hetero-layered structures realized by successive thin film epitaxial growth is in principle constrained by lattice matching prerequisite as well as low yield and expensive production. Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically, bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a dissimilar transition metal dichalcogenide, MoSe2, into scalable hetero-layered hybrids. Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal high visible-light photoreactivity, efficient charge transfer and intimate contact interface for stable cycling and storage purposes. Such a synthetic approach renders independent thickness and composition control anticipated to advance the development of ‘design-and-build' 2D layered heterojunctions for large-scale exploration and applications. PMID:28146147

  17. Self-surface charge exfoliation and electrostatically coordinated 2D hetero-layered hybrids

    NASA Astrophysics Data System (ADS)

    Yang, Min-Quan; Xu, Yi-Jun; Lu, Wanheng; Zeng, Kaiyang; Zhu, Hai; Xu, Qing-Hua; Ho, Ghim Wei

    2017-02-01

    At present, the technological groundwork of atomically thin two-dimensional (2D) hetero-layered structures realized by successive thin film epitaxial growth is in principle constrained by lattice matching prerequisite as well as low yield and expensive production. Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically, bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a dissimilar transition metal dichalcogenide, MoSe2, into scalable hetero-layered hybrids. Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal high visible-light photoreactivity, efficient charge transfer and intimate contact interface for stable cycling and storage purposes. Such a synthetic approach renders independent thickness and composition control anticipated to advance the development of `design-and-build' 2D layered heterojunctions for large-scale exploration and applications.

  18. 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.

  19. 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

    2014-10-04

    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.

  20. Responsive ionic liquid-polymer 2D photonic crystal gas sensors.

    PubMed

    Smith, Natasha L; Hong, Zhenmin; Asher, Sanford A

    2014-12-21

    We developed novel air-stable 2D polymerized photonic crystal (2DPC) sensing materials for visual detection of gas phase analytes such as water and ammonia by utilizing a new ionic liquid, ethylguanidine perchlorate (EGP) as the mobile phase. Because of the negligible ionic liquid vapor pressure these 2DPC sensors are indefinitely air stable and, therefore, can be used to sense atmospheric analytes. 2D arrays of ~640 nm polystyrene nanospheres were attached to the surface of crosslinked poly(hydroxyethyl methacrylate) (pHEMA)-based polymer networks dispersed in EGP. The wavelength of the bright 2D photonic crystal diffraction depends sensitively on the 2D array particle spacing. The volume phase transition response of the EGP-pHEMA system to water vapor or gaseous ammonia changes the 2DPC particle spacing, enabling the visual determination of the analyte concentration. Water absorbed by EGP increases the Flory-Huggins interaction parameter, which shrinks the polymer network and causes a blue shift in the diffracted light. Ammonia absorbed by the EGP deprotonates the pHEMA-co-acrylic acid carboxyl groups, swelling the polymer which red shifts the diffracted light.

  1. 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.

  2. Massively parallel patterning of complex 2D and 3D functional polymer brushes by polymer pen lithography.

    PubMed

    Xie, Zhuang; Chen, Chaojian; Zhou, Xuechang; Gao, Tingting; Liu, Danqing; Miao, Qian; Zheng, Zijian

    2014-08-13

    We report the first demonstration of centimeter-area serial patterning of complex 2D and 3D functional polymer brushes by high-throughput polymer pen lithography. Arbitrary 2D and 3D structures of poly(glycidyl methacrylate) (PGMA) brushes are fabricated over areas as large as 2 cm × 1 cm, with a remarkable throughput being 3 orders of magnitudes higher than the state-of-the-arts. Patterned PGMA brushes are further employed as resist for fabricating Au micro/nanostructures and hard molds for the subsequent replica molding of soft stamps. On the other hand, these 2D and 3D PGMA brushes are also utilized as robust and versatile platforms for the immobilization of bioactive molecules to form 2D and 3D patterned DNA oligonucleotide and protein chips. Therefore, this low-cost, yet high-throughput "bench-top" serial fabrication method can be readily applied to a wide range of fields including micro/nanofabrication, optics and electronics, smart surfaces, and biorelated studies.

  3. Enhanced durability of polymer electrolyte membrane fuel cells by functionalized 2D boron nitride nanoflakes.

    PubMed

    Oh, Keun-Hwan; Lee, Dongju; Choo, Min-Ju; Park, Kwang Hyun; Jeon, Seokwoo; Hong, Soon Hyung; Park, Jung-Ki; Choi, Jang Wook

    2014-05-28

    We report boron nitride nanoflakes (BNNFs), for the first time, as a nanofiller for polymer electrolyte membranes in fuel cells. Utilizing the intrinsic mechanical strength of two-dimensional (2D) BN, addition of BNNFs even at a marginal content (0.3 wt %) significantly improves mechanical stability of the most representative hydrocarbon-type (HC-type) polymer electrolyte membrane, namely sulfonated poly(ether ether ketone) (sPEEK), during substantial water uptake through repeated wet/dry cycles. For facile processing with BNNFs that frequently suffer from poor dispersion in most organic solvents, we non-covalently functionalized BNNFs with 1-pyrenesulfonic acid (PSA). Besides good dispersion, PSA supports efficient proton transport through its sulfonic functional groups. Compared to bare sPEEK, the composite membrane containing BNNF nanofiller exhibited far improved long-term durability originating from enhanced dimensional stability and diminished chronic edge failure. This study suggests that introduction of properly functionalized 2D BNNFs is an effective strategy in making various HC-type membranes sustainable without sacrificing their original adventurous properties in polymer electrolyte membrane fuel cells.

  4. 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.

  5. 11.4% Efficiency non-fullerene polymer solar cells with trialkylsilyl substituted 2D-conjugated polymer as donor

    PubMed Central

    Bin, Haijun; Gao, Liang; Zhang, Zhi-Guo; Yang, Yankang; Zhang, Yindong; Zhang, Chunfeng; Chen, Shanshan; Xue, Lingwei; Yang, Changduk; Xiao, Min; Li, Yongfang

    2016-01-01

    Simutaneously high open circuit voltage and high short circuit current density is a big challenge for achieving high efficiency polymer solar cells due to the excitonic nature of organic semdonductors. Herein, we developed a trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si–C bond interaction. The polymer solar cells obtained by pairing this polymer with a non-fullerene acceptor demonstrated a high power conversion efficiency of 11.41% with both high open circuit voltage of 0.94 V and high short circuit current density of 17.32 mA cm−2 benefitted from the complementary absorption of the donor and acceptor, and the high hole transfer efficiency from acceptor to donor although the highest occupied molecular orbital level difference between the donor and acceptor is only 0.11 eV. The results indicate that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials. PMID:27905397

  6. 11.4% Efficiency non-fullerene polymer solar cells with trialkylsilyl substituted 2D-conjugated polymer as donor

    NASA Astrophysics Data System (ADS)

    Bin, Haijun; Gao, Liang; Zhang, Zhi-Guo; Yang, Yankang; Zhang, Yindong; Zhang, Chunfeng; Chen, Shanshan; Xue, Lingwei; Yang, Changduk; Xiao, Min; Li, Yongfang

    2016-12-01

    Simutaneously high open circuit voltage and high short circuit current density is a big challenge for achieving high efficiency polymer solar cells due to the excitonic nature of organic semdonductors. Herein, we developed a trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si-C bond interaction. The polymer solar cells obtained by pairing this polymer with a non-fullerene acceptor demonstrated a high power conversion efficiency of 11.41% with both high open circuit voltage of 0.94 V and high short circuit current density of 17.32 mA cm-2 benefitted from the complementary absorption of the donor and acceptor, and the high hole transfer efficiency from acceptor to donor although the highest occupied molecular orbital level difference between the donor and acceptor is only 0.11 eV. The results indicate that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials.

  7. 11.4% Efficiency non-fullerene polymer solar cells with trialkylsilyl substituted 2D-conjugated polymer as donor.

    PubMed

    Bin, Haijun; Gao, Liang; Zhang, Zhi-Guo; Yang, Yankang; Zhang, Yindong; Zhang, Chunfeng; Chen, Shanshan; Xue, Lingwei; Yang, Changduk; Xiao, Min; Li, Yongfang

    2016-12-01

    Simutaneously high open circuit voltage and high short circuit current density is a big challenge for achieving high efficiency polymer solar cells due to the excitonic nature of organic semdonductors. Herein, we developed a trialkylsilyl substituted 2D-conjugated polymer with the highest occupied molecular orbital level down-shifted by Si-C bond interaction. The polymer solar cells obtained by pairing this polymer with a non-fullerene acceptor demonstrated a high power conversion efficiency of 11.41% with both high open circuit voltage of 0.94 V and high short circuit current density of 17.32 mA cm(-2) benefitted from the complementary absorption of the donor and acceptor, and the high hole transfer efficiency from acceptor to donor although the highest occupied molecular orbital level difference between the donor and acceptor is only 0.11 eV. The results indicate that the alkylsilyl substitution is an effective way in designing high performance conjugated polymer photovoltaic materials.

  8. Dynamic self-assembly of coordination polymers in aqueous solution.

    PubMed

    Li, Wen; Kim, Yongju; Li, Jingfang; Lee, Myongsoo

    2014-08-07

    The construction of supramolecular polymers has been intensively pursued because the nanostructures formed through weak non-covalent interactions can be triggered by external stimuli leading to smart materials and sensors. Self-assemblies of coordination polymers consisting of metal ions and organic ligands in aqueous solution also provide particular contributions in this area. The main motivation for developing those coordination polymers originates from the value-added combination between metal ions and ligands. This review highlights the recent progress of the dynamic self-assembly of coordination polymers that result from the sophisticated molecular design, towards fabricating stimuli-responsive systems and bio-related materials. Dynamic structural changes and switchable physical properties triggered by various stimuli are summarized. Finally, the outlook for aqueous nanostructures originated from the dynamic self-assembly of coordination polymers is also presented.

  9. 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.

  10. 2D-ELDOR detection of magnetization transfer of nitroxides in disordered solid polymers

    NASA Astrophysics Data System (ADS)

    Maresch, G. G.; Weber, M.; Dubinskii, A. A.; Spiess, H. W.

    1992-05-01

    Two-dimensional electron—electron double resonance (2D-ELDOR) experiments on nitroxide spin labels in solid liquid-crystalline side-group polymers have been performed employing narrow-band microwave excitation pulses followed by a rapid magnetic field step during a mixing time and detection at the new selected point of the EPR spectrum. Information about magnetization transfer throughout the full EPR spectrum is obtained by sweeping both pumping and detecting fields. In the two-dimensional representation of experimental ELDOR data, the different processes causing magnetization transfer through the EPR spectrum, i.e. electron spin diffusion, nuclear relaxation, and slow rotational motions lead to different patterns and can be distinguished by recording 2D-ELDOR spectra as a function of temperature. In the specific system studied, the 2D-ELDOR spectra show the dominance of magnetization transfer between states with close molecular orientations but different nitrogen nuclear spin projections caused by flips of nuclear spins. The results are discussed in terms of dynamic processes in glasses.

  11. Molecular tectonics: design of 2-D networks by simultaneous use of charge-assisted hydrogen and coordination bonds.

    PubMed

    Carpanese, Cristina; Ferlay, Sylvie; Kyritsakas, Nathalie; Henry, Marc; Hosseini, Mir Wais

    2009-11-28

    Using a combination of charge-assisted H- and coordination-bonds, a tetra component system composed of a dicationic and a dianionic organic tecton, Ag(+) cation and XF(6)(-) (X= P, As, Sb) anion behaves as planned and leads to the formation of 2-D isostructural networks for which the energetic contributions of the two recognition events dominate the construction process.

  12. Coordination polymers undergoing spin crossover and reversible ligand exchange in the solid.

    PubMed

    Galet, Ana; Muñoz, M Carmen; Real, José Antonio

    2006-11-04

    Here we report the synthesis and characterisation of a polymer made up of a system of parallel 2-D grids of Fe(II) ions linked by [Au(CN)2]- bridges and its transformation into a new system of three interpenetrated 3-D coordination open frameworks with the NbO topology. Reversibility of this crystal-to-crystal transformation is evidenced by X-ray crystallographic data and from their spin crossover properties.

  13. Quantitative 2D HSQC NMR determination of polymer structures by selecting suitable internal standard references.

    PubMed

    Zhang, Liming; Gellerstedt, Göran

    2007-01-01

    A new analytical method based on the 2D HSQC NMR sequence is presented, which can be applied for quantitative structural determination of complicated polymers. The influence of T1 and T2 relaxations, off-resonance effects, coupling constants and homonuclear couplings are discussed. It was found that the T2 values measured on polymeric samples with the conventional HSQC-CPMG sequence could not be used to correct the errors caused by T2 relaxations during the polarization transfer delay. A unique way of selecting the proper internal standard reference signal(s) is therefore proposed to eliminate the major errors caused by T2 relaxations, resonance offsets, coupling constant deviations and homonuclear couplings. Two polymer samples, a cellulose triacetate and an acetylated lignin, have been used to illustrate the principles. The methodology developed in this work is robust to instrument miss-setting and it can find wide-spread applications in areas where a quantitative analysis of structurally complicated polymers is necessary.

  14. Copper coordination polymers constructed from thiazole-5-carboxylic acid: Synthesis, crystal structures, and structural transformation

    NASA Astrophysics Data System (ADS)

    Meundaeng, Natthaya; Rujiwatra, Apinpus; Prior, Timothy J.

    2017-01-01

    We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu2+ coordination polymers with different dimensionality, namely, 1D [Cu2(5-tza)2(1,10-phenanthroline)2(NO3)2] (1), 2D [Cu(5-tza)2(MeOH)2] (2), and 3D [Cu(5-tza)2]·H2O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza)2]·1.5H2O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air.

  15. 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.

  16. 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

  17. Water linked 3D coordination polymers: Syntheses, structures and applications

    NASA Astrophysics Data System (ADS)

    Singh, Suryabhan; Bhim, Anupam

    2016-12-01

    Three new coordination polymers (CPs) based on Cd and Pb, [Cd(OBA)(μ-H2O)(H2O)]n1, [Pb(OBA)(μ-H2O)]n2 [where OBA=4,4'-Oxybis(benzoate)] and [Pb(SDBA)(H2O)]n.1/4DMF 3 (SDBA=4,4'-Sulfonyldibenzoate), have been synthesized and characterized. The single crystal structural studies reveal that CPs 1 and 2 have three dimensional structure. A water molecule bridges two metal centres which appears to the responsible for the dimensionality increase from 2D to 3D. Compound 3 has a supramolecular 3D structure involving water molecule and hydrogen bonds. A structural transformation is observed when 3 was heated at 100 °C or kept in methanol, forming [Pb(SDBA)]n4. Compound 4 is used as supporting matrix for palladium nanoparticles, PdNPs@4. The PdNPs@4 exhibits good catalytic activity toward the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of NaBH4 at room temperature. Luminescence studies revealed that all CPs could be an effective sensor for nitroaromatic explosives.

  18. Estimation of 3-D pore network coordination number of rocks from watershed segmentation of a single 2-D image

    NASA Astrophysics Data System (ADS)

    Rabbani, Arash; Ayatollahi, Shahab; Kharrat, Riyaz; Dashti, Nader

    2016-08-01

    In this study, we have utilized 3-D micro-tomography images of real and synthetic rocks to introduce two mathematical correlations which estimate the distribution parameters of 3-D coordination number using a single 2-D cross-sectional image. By applying a watershed segmentation algorithm, it is found that the distribution of 3-D coordination number is acceptably predictable by statistical analysis of the network extracted from 2-D images. In this study, we have utilized 25 volumetric images of rocks in order to propose two mathematical formulas. These formulas aim to approximate the average and standard deviation of coordination number in 3-D pore networks. Then, the formulas are applied for five independent test samples to evaluate the reliability. Finally, pore network flow modeling is used to find the error of absolute permeability prediction using estimated and measured coordination numbers. Results show that the 2-D images are considerably informative about the 3-D network of the rocks and can be utilized to approximate the 3-D connectivity of the porous spaces with determination coefficient of about 0.85 that seems to be acceptable considering the variety of the studied samples.

  19. Rbfox2-coordinated alternative splicing of Mef2d and Rock2 controls myoblast fusion during myogenesis

    PubMed Central

    Bland, Christopher S.; Kalsotra, Auinash; Scavuzzo, Marissa A.; Curk, Tomaz; Ule, Jernej; Li, Wei; Cooper, Thomas A.

    2014-01-01

    Summary Alternative splicing plays important regulatory roles during periods of physiological change. During development a large number of genes coordinately express protein isoform transitions regulated by alternative splicing, however, the mechanisms that coordinate splicing and the functional integration of the resultant tissue-specific protein isoforms are typically unknown. Here we show that the conserved Rbfox2 RNA binding protein regulates 30% of the splicing transitions observed during myogenesis and is required for the specific step of myoblast fusion. Integration of Rbfox2-dependent splicing outcomes from RNA-seq with Rbfox2 iCLIP data identified Mef2d and Rock2 as Rbfox2 splicing targets. Restored activities of Mef2d and Rock2 rescued myoblast fusion in Rbfox2 depleted cultures demonstrating functional cooperation of protein isoforms generated by coordinated alterative splicing. The results demonstrate that coordinated alternative splicing by a single RNA binding protein modulates transcription (Mef2d) and cell signaling (Rock2) programs to drive tissue-specific functions (cell fusion) to promote a developmental transition. PMID:25087874

  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. Zinc(II) and Cadmium(II) coordination polymers constructed from phenylenediacetate ligands

    SciTech Connect

    Sezer, Güneş Günay; Yeşilel, Okan Zafer; Erer, Hakan; Şahin, Onur

    2016-01-15

    ABSTRACT: A series of new coordination polymers {[Zn(μ-opda)(μ-bpa)]·2H_2O}{sub n} (1), [Zn(μ{sub 3}-ppda)(μ-bpa)]{sub n} (2), [Cd(μ{sub 3}-ppda)(μ-bpa)]{sub n} (3), [Cd(μ{sub 3}-mpda)(μ-bpa)]{sub n} (4) and [Cd(μ{sub 3}-mpda)(μ-bipy)]{sub n} (5), (o/m/ppda=1,2/1,3/1,4-phenylenediacetate, bpa=1,2-bi(4-pyridyl)ethane, bipy=4,4′-bipyridine) were synthesized. Their structures were characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. Furthermore, the effect of metal sources (zinc acetate and zinc oxide) and acidity of the solution on the structure of the coordination polymers was discussed for complexes 1 and 5, respectively. The single-crystal X-ray crystallographic studies revealed that complexes 1, 3, 4 and 5 are uninodal (4)-connected 2D frameworks and display sql topology with the point symbol of (4{sup 4}.6{sup 2}). Complex 2 is 3D coordination polymer and exhibits pcu topology with the point symbol of (4{sup 12}.6{sup 3}). In addition, the luminescent properties and thermal behavior of all complexes were also investigated. - Graphical abstract: Scheme 1. Topologies of Coordination Polymers Reported in This Paper.

  2. Insight into the crystallization of amorphous imine-linked polymer networks to 2D covalent organic frameworks.

    PubMed

    Smith, Brian J; Overholts, Anna C; Hwang, Nicky; Dichtel, William R

    2016-03-04

    We explore the crystallization of a high surface area imine-linked two-dimensional covalent organic framework (2D COF). The growth process reveals rapid initial formation of an amorphous network that subsequently crystallizes into the layered 2D network. The metastable amorphous polymer may be isolated and resubjected to growth conditions to form the COF. These experiments provide the first mechanistic insight into the mechanism of imine-linked 2D COF formation, which is distinct from that of boronate-ester linked COFs.

  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. 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.

  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. Generalized source method in curvilinear coordinates for 2D grating diffraction simulation

    NASA Astrophysics Data System (ADS)

    Shcherbakov, Alexey A.; Tishchenko, Alexandre V.

    2017-01-01

    The article presents a curvilinear coordinate Fourier space integral method for linear optical rigorous grating diffraction simulation in 3D (crossed grating diffraction). The presented formulation extends our previous work on a related method for 1D periodic grating diffraction. Following this previous work we exploit a concept of the generalized metric sources to efficiently solve the Maxwell's equations. The article provides a general description of the method together with a detailed formulation and analysis of sinusoidal corrugation crossed grating diffraction.

  7. Self-assembly of flexible one-dimensional coordination polymers on metal surfaces.

    PubMed

    Heim, Daniel; Ecija, David; Seufert, Knud; Auwärter, Willi; Aurisicchio, Claudia; Fabbro, Chiara; Bonifazi, Davide; Barth, Johannes V

    2010-05-19

    We employed a de novo synthesized porphyrin module to construct one-dimensional (1D) Cu-coordinated polymers on Cu(111) and Ag(111) surfaces. The programmed geometry and functionality of the molecular module together with its conformational flexibility and substrate interaction yields sinuous metal-organic polymeric assemblies, based on an unusual two-fold Cu-pyridyl coordination motif. An analysis of scanning tunneling microscopy (STM) data reveals the occurrence of two enantiomers, resulting from the surface confinement that deconvolutes the module in 2D-chiral conformational isomers. The stereoisomers exhibit site-specific surface anchoring, from whence three discrete orientations are possible for each species. Their sequence and mutual arrangement determine direction and curvature of the metal-organic chains. The Cu-coordinated polymers are very similar on both Cu(111) and Ag(111), where their formation is induced by intrinsic and coevaporated adatoms, respectively, which indicates that the lateral bonding motif is predominantly independent of the substrate. In addition, molecular manipulation experiments show the collective motion of entire segments of the Cu-coordinated multi-porphyrin polymers.

  8. EXAFS study of some coordination polymers of copper

    NASA Astrophysics Data System (ADS)

    Deshpande, A. P.

    1995-02-01

    The EXAFS spectra for (1) azelaic acid bis phenyl hydrazide, (2) azelaic acid bis 2,4 dinitro phenyl hydrazide and (3) sebacic acid bis phenyl hydrazide coordination polymers of copper were obtained using the EXAFS facility of the Daresbury Laboratory. The EXAFS analysis revealed that copper is surrounded by four nitrogen and two oxygen atoms in the first coordination shell, while the second coordination shell consists of two carbon atoms. This information suggests the octahedral geometry for the repeating units of polymeric complexes, in contrast to the square planar geometry previously proposed.

  9. Protein adsorption resistant surface on polymer composite based on 2D- and 3D-controlled grafting of phospholipid moieties

    NASA Astrophysics Data System (ADS)

    Hoshi, Toru; Matsuno, Ryosuke; Sawaguchi, Takashi; Konno, Tomohiro; Takai, Madoka; Ishihara, Kazuhiko

    2008-11-01

    To prepare the biocompatible surface, a phosphorylcholine (PC) group was introduced on this hydroxyl group generated by surface hydrolysis on the polymer composite composed of polyethylene (PE) and poly (vinyl acetate) (PVAc) prepared by supercritical carbon dioxide. Two different procedures such as two-dimensional (2D) modification and three-dimensional (3D) modification were applied to obtain the steady biocompatible surface. 2D modification was that PC groups were directly anchored on the surface of the polymer composite. 3D modification was that phospholipid polymer was grafted from the surface of the polymer composite by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC). The surfaces were characterized by X-ray photoelectron spectroscopy, dynamic water contact angle measurements, and atomic force microscope. The effects of the poly(MPC) chain length on the protein adsorption resistivity were investigated. The protein adsorption on the polymer composite surface with PC groups modified by 2D or 3D modification was significantly reduced as compared with that on the unmodified PE. Further, the amount of protein adsorbed on the 3D modified surface that is poly(MPC)-grafted surface decreased with an increase in the chain length of the poly(MPC). The surface with an arbitrary structure and the characteristic can be constructed by using 2D and 3D modification. We conclude that the polymer composites of PE/PVAc with PC groups on the surface are useful for fabricating biomedical devices due to their good mechanical and surface properties.

  10. 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.

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

    DOEpatents

    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.

  12. Highly conductive self-assembled nanoribbons of coordination polymers.

    PubMed

    Welte, Lorena; Calzolari, Arrigo; Di Felice, Rosa; Zamora, Felix; Gómez-Herrero, Julio

    2010-02-01

    Organic molecules can self-assemble into well-ordered structures, but the conductance of these structures is limited, which is a disadvantage for applications in molecular electronics. Conductivity can be improved by using coordination polymers-in which metal centres are incorporated into a molecular backbone-and such structures have been used as molecular wires by self-assembling them into ordered films on metal surfaces. Here, we report electrically conductive nanoribbons of the coordination polymer [Pt(2)I(S(2)CCH(3))(4)](n) self-assembled on an insulating substrate by direct sublimation of polymer crystals. Conductance atomic force microscopy is used to probe the electrical characteristics of a few polymer chains ( approximately 10) within the nanoribbons. The observed currents exceed those previously sustained in organic and metal-organic molecules assembled on surfaces by several orders of magnitude and over much longer distances. These results, and the results of theoretical calculations based on density functional theory, confirm coordination polymers as candidate materials for applications in molecular electronics.

  13. 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.

  14. 1D/2D Carbon Nanomaterial-Polymer Dielectric Composites with High Permittivity for Power Energy Storage Applications.

    PubMed

    Dang, Zhi-Min; Zheng, Ming-Sheng; Zha, Jun-Wei

    2016-04-06

    With the development of flexible electronic devices and large-scale energy storage technologies, functional polymer-matrix nanocomposites with high permittivity (high-k) are attracting more attention due to their ease of processing, flexibility, and low cost. The percolation effect is often used to explain the high-k characteristic of polymer composites when the conducting functional fillers are dispersed into polymers, which gives the polymer composite excellent flexibility due to the very low loading of fillers. Carbon nanotubes (CNTs) and graphene nanosheets (GNs), as one-dimensional (1D) and two-dimensional (2D) carbon nanomaterials respectively, have great potential for realizing flexible high-k dielectric nanocomposites. They are becoming more attractive for many fields, owing to their unique and excellent advantages. The progress in dielectric fields by using 1D/2D carbon nanomaterials as functional fillers in polymer composites is introduced, and the methods and mechanisms for improving dielectric properties, breakdown strength and energy storage density of their dielectric nanocomposites are examined. Achieving a uniform dispersion state of carbon nanomaterials and preventing the development of conductive networks in their polymer composites are the two main issues that still need to be solved in dielectric fields for power energy storage. Recent findings, current problems, and future perspectives are summarized.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Chiruta, Daniel; Jureschi, Catalin-Maricel; Linares, Jorge; Garcia, Yann; Rotaru, Aurelian

    2014-02-01

    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.

  17. 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.

  18. 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.

  19. Assembly of two novel Lindqvist polyoxoanion-templated coordination polymers with standard honeycomb cavities

    NASA Astrophysics Data System (ADS)

    Sha, Jingquan; Huang, Lin; Peng, Jun; Pang, Haijun; Tian, Aixiang; Zhang, Pengpeng; Chen, Yuan; Zhu, Min

    2009-02-01

    Two novel polyoxometalate(POM)-templated coordination polymers: [Cu 2(phnz) 3][M 6O 19] (M = Mo for 1, W for 2; phnz = phenazine), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In the compounds, Lindqvist POMs as templates induce the [Cu 2(phnz) 3] complexes to 2D hexagonal metal-organic framework (MOF), which represents 6 3 topologies of dimensions ca. 13.515 × 13.515 × 13.515 Å. Furthermore, the 2D sheets are held together by Lindqvist POMs into 3D supramolecular networks with 1D channel, and Lindqvist POMs site in the channels. The successful syntheses and isolation of two compounds provide a novel example of the utility of POM clusters as templates for self-assembly extended framework with cavities.

  20. Structures and magnetic properties of two noncentrosymmetric coordination polymers based on carboxyphosphinate ligand

    NASA Astrophysics Data System (ADS)

    Li, Jianyong; Xue, Chao-Chao; Liu, Siming; Wang, Zhao-Xi

    2016-11-01

    Two novel coordination polymers have been hydrothermally synthesized by reactions of Cu(II), Mn(II) salt with 2-carboxyethyl(phenyl)phosphinic acid (H2L), namely, [Cu(L)(H2O)]n (1) and [Mn(HL)2]n (2). Both compounds were well characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopic, power X-ray diffraction and magnetic studies. Compound 1 crystallizes in a noncentrosymmetric monoclinic Cc space group and presents an inorganic two-dimensional (2D) network, whereas compound 2 adopts a noncentrosymmetric Pca21 space group and exhibits a 2D layer structure. Magnetic studies reveal a dominant ferromagnetic interaction in 1, and weak antiferromagnetic coupling between the Mn(II) ions in 2 mediated by phosphinico group, respectively.

  1. Synthesis, crystal structure and luminescent properties of one coordination polymer of cadmium(II) with mixed thiocyanate and hexamethylenetetramine ligands.

    PubMed

    Bai, Yan; Shang, Wei-Li; Dang, Dong-Bin; Sun, Ji-De; Gao, Hui

    2009-03-01

    A novel Cd(II) coordination polymer [Cd(SCN)(2)(hmt)(1/2)(H(2)O)](2).H(2)O (hmt=hexamethylenetetramine) has been synthesized and characterized by IR, elemental analysis, TG technique and X-ray crystallography. Cd(II) atom has an distorted octahedral environment with an N(3)S(2)O donor set. Every six Cd(II) centers are linked by hmt and thiocyanato bridges to form a planar 2D coordination polymer containing hexagonal metallocyclic rings [Cd(6)(SCN)(8)(hmt)(2)]. A 2D layer structure is held together with its neighboring ones via a set of hydrogen-bonding interactions to form a 3D supramolecular structure. The luminescent properties of the title complex in the solid state were investigated.

  2. Coordination polymer gels with important environmental and biological applications.

    PubMed

    Jung, Jong Hwa; Lee, Ji Ha; Silverman, Julian R; John, George

    2013-02-07

    Coordination Polymer Gels (CPGs) constitute a subset of solid-like metal ion and bridging organic ligand structures (similar to metal-organic frameworks) that form multi-dimensional networks through a trapped solvent as a result of non-covalent interactions. While physical properties of these gels are similar to conventional high molecular weight organic polymer gels, coordination polymer gel systems are often fully reversible and can be assembled and disassembled in the presence of additional energy (heat, sonication, shaking) to give a solution of solvated gelators. Compared to gels resulting from purely organic self-assembled low molecular weight gelators, metal ions incorporated into the fibrilar networks spanning the bulk solvent can impart CPGs with added functionalities. The solid/liquid nature of the gels allows for species to migrate through the gel system and interact with metals, ligands, and the solvent. Chemosensing, catalysis, fluorescence, and drug-delivery applications are some of the many potential uses for these dynamic systems, taking advantage of the metal ion's coordination, the organic polydentate ligand's orientation and functionality, or a combination of these properties. By fine tuning these systems through metal ion and ligand selection and by directing self-assembly with external stimuli the rational synthesis of practical systems can be envisaged.

  3. Arene Selectivity by a Flexible Coordination Polymer Host

    PubMed Central

    Wright, James S.; Vitórica‐Yrezábal, Iñigo J.; Thompson, Stephen P.

    2016-01-01

    Abstract The coordination polymers [Ag4(O2CCF3)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(O2CCF3)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

  4. Polymer Membranes with Vertically Oriented Pores Constructed by 2D Freezing at Ambient Temperature.

    PubMed

    Liang, Hong-Qing; Ji, Ke-Jia; Zha, Li-Yun; Hu, Wen-Bing; Ou, Yang; Xu, Zhi-Kang

    2016-06-08

    Polymer membranes with well-controlled and vertically oriented pores are of great importance in the applications for water treatment and tissue engineering. On the basis of two-dimensional solvent freezing, we report environmentally friendly facile fabrication of such membranes from a broad spectrum of polymer resources including poly(vinylidene fluoride), poly(l-lactic acid), polyacrylonitrile, polystyrene, polysulfone and polypropylene. Dimethyl sulfone, diphenyl sulfone, and arachidic acid are selected as green solvents crystallized in the polymer matrices under two-dimensional temperature gradients induced by water at ambient temperature. Parallel Monte Carlo simulations of the lattice polymers demonstrate that the directional process is feasible for each polymer holding suitable interaction with a corresponding solvent. As a typical example of this approach, poly(vinylidene fluoride) membranes exhibit excellent tensile strength, high optical transparence, and outstanding separation performance for the mixtures of yeasts and lactobacilli.

  5. 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.

  6. Non-Fullerene Polymer Solar Cells Based on Alkylthio and Fluorine Substituted 2D-Conjugated Polymers Reach 9.5% Efficiency.

    PubMed

    Bin, Haijun; Zhang, Zhi-Guo; Gao, Liang; Chen, Shanshan; Zhong, Lian; Xue, Lingwei; Yang, Changduk; Li, Yongfang

    2016-04-06

    Non-fullerene polymer solar cells (PSCs) with solution-processable n-type organic semiconductor (n-OS) as acceptor have seen rapid progress recently owing to the synthesis of new low bandgap n-OS, such as ITIC. To further increase power conversion efficiency (PCE) of the devices, it is of a great challenge to develop suitable polymer donor material that matches well with the low bandgap n-OS acceptors thus providing complementary absorption and nanoscaled blend morphology, as well as suppressed recombination and minimized energy loss. To address this challenge, we synthesized three medium bandgap 2D-conjugated bithienyl-benzodithiophene-alt-fluorobenzotriazole copolymers J52, J60, and J61 for the application as donor in the PSCs with low bandgap n-OS ITIC as acceptor. The three polymers were designed with branched alkyl (J52), branched alkylthio (J60), and linear alkylthio (J61) substituent on the thiophene conjugated side chain of the benzodithiophene (BDT) units for studying effect of the substituents on the photovoltaic performance of the polymers. The alkylthio side chain, red-shifted absorption down-shifted the highest occupied molecular orbital (HOMO) level and improved crystallinity of the 2D conjugated polymers. With linear alkylthio side chain, the tailored polymer J61 exhibits an enhanced JSC of 17.43 mA/cm(2), a high VOC of 0.89 V, and a PCE of 9.53% in the best non-fullerene PSCs with the polymer as donor and ITIC as acceptor. To the best of our knowledge, the PCE of 9.53% is one of the highest values reported in literature to date for the non-fullerene PSCs. The results indicate that J61 is a promising medium bandgap polymer donor in non-fullerene PSCs.

  7. Development of a 2-D large-scale micellar/polymer simulator

    SciTech Connect

    Wang, B.

    1982-01-01

    A large-scale, two-dimensional, multicomponent, multiphase, compositional simulator for micellar/polymer flooding has been developed and applied. It can be used to calculate the areal sweep with any well pattern and any irregular reservoir boundary. This model involves both streamline and finite-difference techniques. Time invariant streamlines without transverse dispersion are assumed. The change in the flow rates into each streamline is accounted for as a function of mobility ratio. The sensitivity of the oil recovery for micellar/polymer flood to several reservoir and process variables was investigated. The reservoir variables included the well spacing, pattern type, pattern orientation in an anisotropic reservoir, and degree of confinement. The process variables included the salinity gradient, surfactant content of the slug, slug and polymer bank sizes, mobility ratio of polymer drive to oil bank, and polymer shear thinning effect. In order to demonstrate that this model is capable of handling large field problems, a large-scale simulation of the north lease of the El Dorado micellar/polymer pilot test was made. The simulated final oil recovery and the production histories of each producer are illustrated.

  8. 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.

  9. Stabilization of 2D assemblies of silver nanoparticles by spin-coating polymers

    NASA Astrophysics Data System (ADS)

    Hu, Longyu; Pfirman, Aubrie; Chumanov, George

    2015-12-01

    Silver nanoparticles self-assembled on poly(4-vinylpyridine) modified surfaces were spin-coated with poly(methyl methacrylate), poly(butyl methacrylate) and polystyrene from anisole and toluene solutions. The polymers filled the space between the particles thereby providing stabilization of the assemblies against particle aggregation when dried or chemically modified. The polymers did not coat the top surface of the nanoparticles offering the chemical accessibility to the metal surface. This was confirmed by converting the stabilized nanoparticles into silver sulfide and gold clusters. Etching the nanoparticles resulted in crater-like polymeric structures with the cavities extending down to the underlying substrate. Electrochemical reduction of silver inside the craters was performed. The approach can be extended to other nanoparticle assemblies and polymers.

  10. 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.

  11. Thermal- and pressure-induced cooperative spin transition in the 2D and 3D coordination polymers {Fe(5-Br-pmd)z[M(CN)x]y} (M=AgI, AuI, NiII, PdII, PtII).

    PubMed

    Agustí, Gloria; Gaspar, Ana Belén; Muñoz, M Carmen; Real, José Antonio

    2007-11-12

    A new family of cyanide-based spin-crossover polymers with the general formula {Fe(5-Br-pmd)z[M(CN)x]y} [M=AgI (1), AuI (2), NiII (3), PdII (4), PtII (5); 5-Br-pmd=5-bromopyrimidine; z=1 or 2, x=2 or 4, and y=2 or 1] have been synthesized and characterized using single-crystal X-ray diffraction (XRD), X-ray powder diffraction (XRPD), magnetic susceptibility measurements, and differential scanning calorimetry (DSC). At 293 K, compound 1 presents the monoclinic space group C2/c, whereas at 120 K, it changes to the monoclinic space group P21/c. At 293 K, the crystal structure of 1 displays an uninodal three-dimensional network whose nodes, constituted of FeII, lie at the inversion center of an elongated octahedron. The equatorial bond lengths are defined by the N atoms of four [AgI(CN)2]- groups belonging to two crystallographically nonequivalent AgI atoms, Ag(1) and Ag(2). They are shorter than those of the axial positions occupied by the N atoms of the 5-Br-pmd ligands. The Fe-N average bond length of 2.1657(7) A is consistent with a high-spin (HS) state for the FeII ions. At 120 K, the crystal structure changes refer mainly to the FeII environment. There are two crystallographically independent FeII ions at this temperature, Fe(1) and Fe(2), which adopt the HS and low-spin (LS) states, respectively. The average Fe-N bond length for Fe(1) [2.174(5) A] and Fe(2) [1.955(5) A] agrees well with the reported magnetic data at this temperature. The spin transition of the FeII ions labeled as Fe(1) is found to be centered at Tc downward arrow=149 K and Tc upward arrow=167 K and accompanied by a drastic change of color from orange (HS) to red (LS). Magnetic susceptibility measurements under applied hydrostatic pressure performed on 1 have shown a linear displacement of the transition to higher temperatures while the hysteresis width remains unaltered in the interval of pressures of 105 Pa to 0.34 GPa. A further increase of the pressure induces the spin transition in the Fe(2

  12. 2D spatially controlled polymer micro patterning for cellular behavior studies

    NASA Astrophysics Data System (ADS)

    Dinca, V.; Palla-Papavlu, A.; Paraico, I.; Lippert, T.; Wokaun, A.; Dinescu, M.

    2011-04-01

    A simple and effective method to functionalize glass surfaces that enable polymer micropatterning and subsequent spatially controlled adhesion of cells is reported in this paper. The method involves the application of laser induced forward transfer (LIFT) to achieve polymer patterning in a single step onto cell repellent substrates (i.e. polyethyleneglycol (PEG)). This approach was used to produce micron-size polyethyleneimine (PEI)-patterns alternating with cell-repellent areas. The focus of this work is the ability of SH-SY5Y human neuroblastoma cells to orient, migrate, and produce organized cellular arrangements on laser generated PEI patterns.

  13. 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.

  14. Chemistry and application of flexible porous coordination polymers*

    PubMed Central

    Bureekaew, Sareeya; Shimomura, Satoru; Kitagawa, Susumu

    2008-01-01

    Porous coordination polymers (PCPs), which are microporous materials, have been given much attention from both scientific and commercial aspects regarding their application to gas storage, gas separation and catalytic reaction because of the regularity of their pore shape and pore size, accompanied with the functionality. Moreover, in recent years, flexible PCPs, which are structurally transformable depending upon external stimuli, have been attractive because they provide unique properties, dissimilar to those of zeolites. In this review, the chemistry and application of flexible crystalline PCPs are summarized and discussed. PMID:27877934

  15. Functional 2D nanoparticle/polymer array: Interfacial assembly, transfer, characterization, and coupling to photonic crystal cavities

    NASA Astrophysics Data System (ADS)

    Xiong, Shisheng

    We developed a universal, facile and robust method to prepare free-standing, ordered and patternable nanoparticle/polymer monolayer arrays by evaporation-induced self-assembly at a fluid interface. The ultra-thin monolayer nanoparticle/polymer arrays are sufficiently robust that they can be transferred to arbitrary substrates, even with complex topographies. More importantly, the Poly (methyl methacrylate) (PMMA) in the system serves as a photoresist enabling two modes of electron beam (e-beam) nanoparticle patterning. These ultra-thin films of monolayer nanoparticle arrays are of fundamental interest as 2D artificial solids for electronic, magnetic and optical properties and are also of technological interest for a diverse range of applications in micro- and macro-scale devices including photovoltaics, sensors, catalysis, and magnetic storage. By co-assembly with block co-polymers, the nanoparticles were selectively positioned in one specific phase, representing a high throughput route for creating nanoparticle patterns. The self-assembly process was investigated by combined in-situ grazing incidence small angle x-ray scattering (GISAXS) and numerical simulation. By e-beam irradiation of free-standing 2D NP/polymer arrays, anisotropic nanowire arrays have been fabricated. Additionally, preliminary investigation on assembly of binary nanoparticle arrays has also been introduced, serving as promising future directions of interfacial assembly. Controlling the rate of spontaneous emission and thus promoting the photon generation efficiency is a key step toward fabrication of Quantum dot based single-photon sources, and harnessing of light energy from emitters with a broad emitting spectrum. Coupling of photo emitters to photonic cavities without perturbing the optical performance of cavities remains as a challenge in study of Purcell effect based on quantum electrodynamics. Taking advantage of interfacial assembly and transfer, we have achieved controlled deposition

  16. Sub-60 mV/decade switching in 2D negative capacitance field-effect transistors with integrated ferroelectric polymer

    NASA Astrophysics Data System (ADS)

    McGuire, Felicia A.; Cheng, Zhihui; Price, Katherine; Franklin, Aaron D.

    2016-08-01

    There is a rising interest in employing the negative capacitance (NC) effect to achieve sub-60 mV/decade (below the thermal limit) switching in field-effect transistors (FETs). The NC effect, which is an effectual amplification of the applied gate potential, is realized by incorporating a ferroelectric material in series with a dielectric in the gate stack of a FET. One of the leading challenges to such NC-FETs is the variable substrate capacitance exhibited in 3D semiconductor channels (bulk, Fin, or nanowire) that minimizes the extent of sub-60 mV/decade switching. In this work, we demonstrate 2D NC-FETs that combine the NC effect with 2D MoS2 channels to extend the steep switching behavior. Using the ferroelectric polymer, poly(vinylidene difluoride-trifluoroethylene) (P(VDF-TrFE)), these 2D NC-FETs are fabricated by modification of top-gated 2D FETs through the integrated addition of P(VDF-TrFE) into the gate stack. The impact of including an interfacial metal between the ferroelectric and dielectric is studied and shown to be critical. These 2D NC-FETs exhibit a decrease in subthreshold swing from 113 mV/decade down to 11.7 mV/decade at room temperature with sub-60 mV/decade switching occurring over more than 4 decades of current. The P(VDF-TrFE) proves to be an unstable option for a device technology, yet the superb switching behavior observed herein opens the way for further exploration of nanomaterials for extremely low-voltage NC-FETs.

  17. Adsorption mechanism at the molecular level between polymers and uremic octapeptide by the 2D 1H NMR Technique.

    PubMed

    Li, Guohua; Li, Jihong; Wang, Wei; Yang, Mei; Zhang, Yuanwei; Sun, Pingchuan; Yuan, Zhi; He, Binglin; Yu, Yaoting

    2006-06-01

    To remove uremic octapeptide from the blood stream of uremic patients, various modified polyacylamide cross-linked absorbents were prepared. Adsorption experiments showed these absorbents have significant differences in adsorption capacity to the target peptide. In this paper, two-dimension proton nuclear magnetic resonance (2D 1H NMR) spectroscopy was used to investigate the interaction mechanism between the peptide and the adsorbents. Because of the insolubility of the absorbent, some soluble linear polymers with the same functional groups as the absorbents were employed as the model adsorbents in 2D 1H NMR. The preferred binding site for the peptide and polymers was identified to be at the C-terminal carboxyl group of the octapeptide via chemical shift perturbation effects. In this study, we found that hydrogen bonding, electrostatic, and hydrophobic interactions all play a role in the interaction force but had different contributions. Especially, the great chemical shift changes of the aromatic amino acid residues (Trp) during the interaction between butyl-modified polyacrylamide and octapeptide suggested the hydrophobic interaction, incorporated with the electrostatic force, played an important role in the binding reaction in aqueous solutions. This information not only rationally explained the results of the adsorption experiments, but also identified the effective binding site and mechanism, and shall provide a structural basis for designing better affinity-type adsorbents for the target peptide.

  18. 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}.

  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. Interfacial polymerization of conductive polymers: Generation of polymeric nanostructures in a 2-D space.

    PubMed

    Dallas, Panagiotis; Georgakilas, Vasilios

    2015-10-01

    In the recent advances in the field of conductive polymers, the fibrillar or needle shaped nanostructures of polyaniline and polypyrrole have attracted significant attention due to the potential advantages of organic conductors that exhibit low-dimensionality, uniform size distribution, high crystallinity and improved physical properties compared to their bulk or spherically shaped counterparts. Carrying the polymerization reaction in a restricted two dimensional space, instead of the three dimensional space of the one phase solution is an efficient method for the synthesis of polymeric nanostructures with narrow size distribution and small diameter. Ultra-thin nanowires and nanofibers, single crystal nanoneedles, nanocomposites with noble metals or carbon nanotubes and layered materials can be efficiently synthesized with high yield and display superior performance in sensors and energy storage applications. In this critical review we will focus not only on the interfacial polymerization methods that leads to polymeric nanostructures and composites and their properties, but also on the mechanism and the physico-chemical processes that govern the diffusion and reactivity of molecules and nanomaterials at an interface. Recent advances for the synthesis of conductive polymer composites with an interfacial method for energy storage applications and future perspectives are presented.

  1. Assembly of three coordination polymers based on a sulfonic-carboxylic ligand showing high proton conductivity.

    PubMed

    Zhao, Shu-Na; Song, Xue-Zhi; Zhu, Min; Meng, Xing; Wu, Lan-Lan; Song, Shu-Yan; Wang, Cheng; Zhang, Hong-Jie

    2015-01-21

    Three new coordination polymers (CPs)/metal-organic frameworks (MOFs) with different structures have been synthesized using 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (H4L) and metal ions, Cu(2+), Ca(2+) and Cd(2+). The Cu compound features a one-dimensional chain structure, further extending into a 2D layer network through H-bond interactions. Both the Ca and Cd compounds show 3D frameworks with (4,4)-connected PtS-type topology and (3,6)-connected bct-type topology, respectively. These CPs/MOFs all exhibit proton conduction behavior, especially for the Cu compound with a proton conductivity of 3.46 × 10(-3) S cm(-1) at 368 K and 95% relative humidity (RH). Additionally, the activation energy (Ea) has also been investigated to deeply understand the proton-conduction mechanism.

  2. Syntheses and structures of three transition metal coordination polymers based on 5-Aminonicotinic acid

    NASA Astrophysics Data System (ADS)

    Jiang, Ya-Hui; Wu, Wei-Ping; Yang, Guo-Ping; Jin, Jun-Cheng; Xi, Zheng-Ping; Wang, Yao-Yu

    2015-07-01

    Three new coordination polymers (CPs) based on rigid ligand 5-Aminonicotinic acid (5-anaH), [Cd(5-ana)2]·(H2O)2 (1), [Cd(5-ana)(HCOO) ] (2) and [Cu(5-ana)2] (3), have been synthesized under different solvent media and temperatures. All CPs are characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, powder X-ray diffraction and thermogravimetric analysis. Compound 1 is a two-dimensional (2D) (4,4)-connected layered structure contains 1D open channels. 2 shows a 2-nodal (3,5)-connected three-dimensional (3D) framework with {52·6}{53·63·73·8} topology. While 3 displays a 3D (3,6)-connected homochiral framework with {42·6}2{44·62·85·104} topology. The solid-state photoluminescence for 1 and 2 were also studied.

  3. Microchannel refill: a new method for fabricating 2D nanochannels in polymer substrates.

    PubMed

    Li, Jing-min; Liu, Chong; Ke, Xue; Xu, Zheng; Duan, Ya-jie; Fan, Yan; Li, Meng; Zhang, Kai-ping; Wang, Li-ding

    2012-10-21

    In this paper, we present a new approach that is capable of fabricating nanochannels in a poly(methyl methacrylate) (PMMA) substrate. This method, which we call microchannel refill (MR), utilizes the refilling of glassy thermoplastics under thermal compression to reduce a microscopic channel to a nanochannel. It only has two main steps. First, a microchannel is fabricated in a PMMA substrate using normal hot embossing. Second, the microchannel is compressed under a certain temperature and pressure to obtain a nanochannel. We show that a nanochannel with a width as small as 132 nm (with a depth of 85 nm) can be easily produced by choosing the appropriate compression temperature, compression pressure, original microchannel width and original microchannel aspect ratio. Compared with most current nanochannel fabrication methods, MR is a quick, simple and cost-effective way to produce nanochannels in polymer substrates.

  4. 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.

  5. Conductive polymer-mediated 2D and 3D arrays of Mn3O4 nanoblocks and mesoporous conductive polymers as their replicas.

    PubMed

    Nakagawa, Yoshitaka; Kageyama, Hiroyuki; Matsumoto, Riho; Oaki, Yuya; Imai, Hiroaki

    2015-11-28

    Orientation-controlled 2D and 3D microarrays of Mn3O4 nanocuboids that were mediated by a conductive polymer were fabricated by evaporation-induced self-assembly of the oxide nanoblocks and subsequent polymerization of pyrrole in the interparticle spaces. Free-standing mesoporous polypyrroles (PPy) having chain- and square-grid-like nanovoid arrays were obtained as replicas of the composite assemblies by dissolving the oxide nanoblocks. The PPy-mediated manganese oxide arrays exhibited stable electrochemical performance as an ultrathin anode of a lithium-ion secondary battery.

  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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. A framework for predicting surface areas in microporous coordination polymers.

    PubMed

    Schnobrich, Jennifer K; Koh, Kyoungmoo; Sura, Kush N; Matzger, Adam J

    2010-04-20

    A predictive tool termed the linker to metal cluster (LiMe) ratio is introduced as a method for understanding surface area in microporous coordination polymers (MCPs). Calibrated with geometric accessible surface area computations, the LiMe ratio uses molecular weight of building block components to indicate the maximum attainable surface area for a given linker and metal cluster combination. MOF-5 and HKUST-1 are used as prototypical structures to analyze MCPs with octahedral M(4)O(CO(2)R)(6) and paddlewheel M(2)(CO(2)R)(4) metal clusters. Insight into the effects of linker size, geometry, number of coordinating groups, and framework interpenetration is revealed through the LiMe ratio analysis of various MCPs. Experimental surface area deviation provides indication that a material may suffer from incomplete guest removal, structural collapse, or interpenetration. Because minimal data input are required, the LiMe ratio surface area analysis is suggested as a quick method for experimental verification as well as a guide for the design of new materials.

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

    SciTech Connect

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

    2015-11-15

    A couple of Mg(II)-based coordination polymer enantiomers [MgL(DMF)(H{sub 2}O){sub 3}]{sub n} (R-MgL and S-MgL), and a Zn(II)-based coordination polymer [ZnL(DMF)]{sub 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 (H{sub 2}L) 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 P2{sub 1} 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. - Highlights: • A couple of Mg(II)-based enantiomers were obtained as the racemic conglomerate. • The ligand is 4,4′-(9,9-dimethyl-9H-fluorene-2,7-diyl)dibenzoic acid. • MgL features the right- or left-handed homochiral 1D Mg–O–C helical chain. • ZnL features the 1D Zn–O–C meso-helical chain. • Both MgL and ZnL display the intense solid-state blue emissions.

  13. Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

    PubMed

    Lee, Hosoowi; Jeong, Young-Hwan; Kim, Joo-Ho; Kim, Inhye; Lee, Eunji; Jang, Woo-Dong

    2015-09-30

    We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 μM) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased

  14. New 4-carboxylphthalhydrazidate-bridged Mn2+/In3+ coordination polymers

    NASA Astrophysics Data System (ADS)

    Jin, Juan; Yan, Wen-Fu; Yu, Xiao-Yang; Yang, Qing-Feng; Liu, Bing; Xu, Ji-Qing; Gao, Shan-Min; Li, Chuan-Zhao; Lin, Chen

    2017-04-01

    Based on the hydrothermal in situ acylation reaction of benzene-1,2,4-tricarboxylic acid (btca) with N2H4·H2O, two containing-4-carboxylphthalhydrazidate Mn2+/In3+ coordination polymers, [Mn(cpth)(phen)] 1 and [In(cpth)(ox)0.5(phen)]·H2O 2 (cpth = 4-carboxylphthalhydrazidate, phen = 1,10-phenanthroline, ox = oxalate), were obtained and characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. In compound 1, the cpth ligands exhibit a μ4-bridging mode, which link Mn(II) centers into a 2-D layer structure with ancillary phen molecules. In compound 2, the cpth ligands exhibit a μ2-bridging mode, which link In(III) centers into a binuclear unit. Ox ligands act as the second linkers, extending binuclear unit into a 1-D chain with ancillary phen molecules. Via Nsbnd H⋯O interactions, compound 2 self-assembles into a 2-D supramolecular layer. The magnetic analysis indicates that there exists antiferromagnetic interactions between magnetic centers in compound 1. The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution.

  15. 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

  16. 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.

  17. Two Ag(I) coordination polymers derived from melamine and dicarboxylates: Syntheses, crystal structures and thermal stabilities

    NASA Astrophysics Data System (ADS)

    Li, Yun-Hua; Sun, Di; Luo, Geng-Geng; Liu, Fu-Jing; Hao, Hong-Jun; Wen, Yi-Mei; Zhao, Yang; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-08-01

    Two mixed-ligand Ag(I) coordination polymers (CPs), [(NH 4)Ag 3(MA) 2(suc) 2] n ( 1), [Ag 2(MA) 2(adip)·CH 3OH·H 2O] n ( 2), (where MA = melamine, H 2suc = succinic acid, H 2adip = adipic acid) have been synthesized and structurally characterized by element analysis, IR and X-ray single-crystal diffraction. The CP 1 is a three-dimensional (3D) framework in which the MA acts as a tridentate ligand and suc 2- anion shows three types of coordination modes. Each Ag(I) ion acts as a 4-connected node to generate three- and six-membered cycles, as a result, the network can be simplified to be an overall multi-layered Kagomé topology. The CP 2 is a 2D single-layer structure constructed by tridentate MA ligands and adip 2- anions. The adjacent single-layers are inter-linked to form a double-layer 2D structure through the Ag⋯Ag interactions. Two CPs structurally vary from 2D sheet to 3D framework, which indicates that the different dicarboxylates and coordination modes of MA ligand have significant influence on the final structures. Moreover, the thermal stabilities of them were also discussed.

  18. Molecular tectonics: formation and structural studies on a 2-D directional coordination network based on a non-centric metacyclophane based tecton and zinc cation.

    PubMed

    Ehrhart, Jérôme; Planeix, Jean-Marc; Kyritsakas-Gruber, Nathalie; Hosseini, Mir Wais

    2010-02-28

    The combination of tectons based on the [1111]metacyclophane backbone blocked the 1,3-alternate conformation bearing two imidazoly or pyrazolyl groups located on the same side with metal halide complexes leads to the formation of either discrete metallmacrobicycles or infinite 1-D coordination networks. The same backbone bearing two sets of two different coordinating poles composed of two pyridyl and two pyrazolyl units, owing to its non-centrosymmetric nature, forms a directional 2-D network packed in an anti-parallel fashion.

  19. Syntheses and structural studies of coordination polymers with microporous frameworks

    NASA Astrophysics Data System (ADS)

    Niu, Tianyan

    The purpose of this work is to synthesize microporous solids using coordination chemistry. The syntheses were carried by diffusion method. Starting reagents, solvent, concentration, reaction speed and time, and temperature were the variables used to optimize the syntheses. The resulting products were characterized by single crystal X-ray diffraction to determine their structures. X-ray powder diffraction, TGA, IR, elemental analysis, and electron microprobe were used to provide complementary or supporting information. Exploratory studies were carried out mainly on organotin-cyanometalate compounds [(RmSnIV)x{M(CN)n} y]. The compounds are made up of SnRm cations and M(CN) n anions. The structures adopted are determined by the number and size of the organic ligands attached to the Sn atoms and by the cyanometalate M(CN) n moiety. Several new compounds in this class were synthesized and structurally characterized. They are [(Bu3Sn)3M(CN)6] (M = Fe, Co), [(R2Sn)3{CO(CN)6}2·X] (R = vinyl, butyl, and propyl), and [(Ph3Sn)2Ni(CN) 4 Ph3SnOH·˜0.8CH3CN·˜0.2H 2O]. The compound [(Ph3Sn)2Ni(CN)4·Ph 3SnOH·˜0.8CH3CN·˜0.2H2O] is to our knowledge, the first three dimensional cyanometalate coordination polymer with expanded inorganic NbO structure. The framework is not interpenetrated and the large central cavity in the structure is filled by inclusion of Ph 3SnOH and other solvent molecules during synthesis. In addition to the investigation of organotin-cyanometalate compounds, other approaches to microporous solids were also studied. A new compound [Co(H 2O)2Ni(CN)4·4H2O] in the Hofmann's clathrate family was obtained. Five one dimensional polymers synthesized by the reaction of dirhodium(II) tetraacetate with 1,4-dicyanobenzene in different solvent systems were also synthesized, and the effect of solvent on the resulting structures was investigated.

  20. 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.

  1. Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication.

    PubMed

    Reboul, Julien; Furukawa, Shuhei; Horike, Nao; Tsotsalas, Manuel; Hirai, Kenji; Uehara, Hiromitsu; Kondo, Mio; Louvain, Nicolas; Sakata, Osami; Kitagawa, Susumu

    2012-06-24

    The spatial organization of porous coordination polymer (PCP) crystals into higher-order structures is critical for their integration into separation systems, heterogeneous catalysts, ion/electron transport and photonic devices. Here, we demonstrate a rapid method to spatially control the nucleation site, leading to the formation of mesoscopic architecture made of PCPs, in both two and three dimensions. Inspired by geological processes, this method relies on the morphological replacement of a shaped sacrificial metal oxide used both as a metal source and as an 'architecture-directing agent' by an analogous PCP architecture. Spatiotemporal harmonization of the metal oxide dissolution and the PCP crystallization allowed the preservation of very fine mineral morphological details of periodic alumina inverse opal structures. The replication of randomly structured alumina aerogels resulted in a PCP architecture with hierarchical porosity in which the hydrophobic micropores of the PCP and the mesopores/macropores inherited from the parent aerogels synergistically enhanced the material's selectivity and mass transfer for water/ethanol separation.

  2. 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

  3. 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.

  4. Copper(II) coordination polymers derived from triethanolamine and pyromellitic acid for bioinspired mild peroxidative oxidation of cyclohexane.

    PubMed

    Karabach, Yauhen Y; Kirillov, Alexander M; Haukka, Matti; Kopylovich, Maximilian N; Pombeiro, Armando J L

    2008-01-01

    The new inorganic 1D coordination polymer [Cu2(H3tea)2(mu4-pma)]n has been prepared, via self-assembly in aqueous medium, from copper(II) nitrate, triethanolamine (H3tea), pyromellitic acid (H4pma) and lithium hydroxide, and characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses. This compound and the related 2D polymer [Cu2(mu-H2tea)(2){mu3-Na2(H2O)4}(mu6-pma)]n.10nH2O are shown to mimic the alkane partial oxidation activity of the multicopper particulate methane monooxygenase, acting as catalysts precursors for the peroxidative oxidation of cyclohexane into cyclohexanol and cyclohexanone, by hydrogen peroxide (as green oxidant) and at room temperature in acidic MeCN/H2O medium. An overall yield (based on cyclohexane) of 29% has been achieved.

  5. 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.

  6. Metal Coordination Polymers as Potential High-Energy Lithographic Resists

    DTIC Science & Technology

    1989-05-15

    resists,I ~ ~ ~ 1-&obalt polymers--- - dfiroiuinpIrms (CotiueC-positive6 resjits ,-beta- diketones 19 At8tTRACT (Cniu nreverse ifnecessary and odentify by...have synthesized several cobalt(III) coordi- nation polymers, one of which was briefly described earlier (5,6). The general synthesis for three... diketones from ad- jacent units in the polymer chains. The corresponding sulfone polymer can be synthesized from the oxidation of the sulfoxide

  7. Synthesis, characterization, monolayer assembly and 2D lanthanide coordination of a linear terphenyl-di(propiolonitrile) linker on Ag(111).

    PubMed

    Chen, Zhi; Klyatskaya, Svetlana; Urgel, José I; Écija, David; Fuhr, Olaf; Auwärter, Willi; Barth, Johannes V; Ruben, Mario

    2015-01-01

    As a continuation of our work employing polyphenylene-dicarbonitrile molecules and in particular the terphenyl derivative 1 (TDCN), we have synthesized a novel ditopic terphenyl-4,4"-di(propiolonitrile) (2) linker for the self-assembly of organic monolayers and metal coordination at interfaces. The structure of the organic linker 2 was confirmed by single crystal X-ray diffraction analysis (XRD). On the densely packed Ag(111) surface, the terphenyl-4,4"-di(propiolonitrile) linkers self-assemble in a regular, molecular chevron arrangement exhibiting a Moiré pattern. After the exposure of the molecular monolayer to a beam of Gd atoms, the propiolonitrile groups get readily involved in metal-ligand coordination interactions. Distinct coordination motifs evolve with coordination numbers varying between three and six for the laterally-bound Gd centers. The linker molecules retain an overall flat adsorption geometry. However, only networks with restricted local order were obtained, in marked contrast to previously employed, simpler polyphenylene-dicarbonitrile 1 linkers.

  8. Molecular tectonics: p-H-thiacalix[4]arene pyridyl appended positional isomers as tectons for the formation of 1D and 2D mercury coordination networks.

    PubMed

    Ovsyannikov, A; Ferlay, S; Solovieva, S E; Antipin, I S; Konovalov, A I; Kyritsakas, N; Hosseini, M W

    2013-07-21

    Three p-H-thiacalix[4]arene pyridyl appended coordinating tectons (2-4) in a 1,3-alternate conformation have been prepared and structurally characterised in the solid state. These compounds are positional isomers differing only by the position of the nitrogen atom on the pyridyl ring. Their combinations with HgCl2 lead to the formation of 1- and 2-D neutral mercury coordination networks. Whereas for tecton 2 (ortho isomer) a 2D architecture resulting from the bridging of consecutive tectons by the mononuclear HgCl2 unit is obtained, for tecton 3 (meta isomer) again a 2D network is formed. However, in that case, the interconnection of consecutive organic tectons 3 takes place through a binuclear Hg2Cl4 species. Finally, in the case of tecton 4 (para position), a 1D ribbon type double chain arrangement resulting from the bridging of consecutive tectons by trinuclear Hg3Cl6 units followed by the interconnection of two chains through the fusion of the trinuclear centres into a hexanuclear node is observed.

  9. Effective Photo- and Triboluminescent Europium(III) Coordination Polymers with Rigid Triangular Spacer Ligands.

    PubMed

    Hasegawa, Yasuchika; Tateno, Shiori; Yamamoto, Masanori; Nakanishi, Takayuki; Kitagawa, Yuichi; Seki, Tomohiro; Ito, Hajime; Fushimi, Koji

    2017-02-21

    Luminescent Eu(III) coordination polymers with rigid triangular spacer ligands are reported. The Eu(III) coordination polymer, [Eu3 (hfa)9 (tppb)2 ]n (hfa: hexafluoroacetylacetonate, tppb: tris(4-diphenylphosphorylphenyl)benzene), shows high thermo-stability (decomposition temperature=354 °C) and photoluminescence quantum yield (Φ4f-4f =82 %, photosensitized energy transfer efficiency=78 %). The triboluminescence efficiency of Eu(III) coordination polymer with triangular spacers under laser pulse irradiation (Nd:YAG, λ=1064 nm, pulse width=5 ns, pulse energy=0.1 mJ) is calculated to be 49 %. Characteristic triangular structure, high emission quantum yield, effective photosensitized energy transfer, and remarkable triboluminescence properties of Eu(III) coordination polymers are demonstrated for the first time.

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

    SciTech Connect

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

    2016-03-15

    Six Ln–Ag coordination polymers {[LnAg_2(IN)_4(H_2O)_5]·NO_3·2H_2O}{sub n} (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg_2(IN)_4(H_2O)_2]·NO_3·H_2O}{sub n} (3), [LnAg(pdc){sub 2}]{sub n} (Ln=Eu(4) and Pr (5), H{sub 2}pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc){sub 2}(H{sub 2}O){sub 4}]{sub n} (6) (H{sub 2}bidc=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. - Graphical abstract: Six Ag–Ln coordination polymers have been hydrothermally synthesized and characterized. The photoluminescence properties were studied. The distortion of coordination geometry of Ag(I) ion affect structure framework. Introduction of Ag(I) cause wonderful changes to the NIR emission of Ln(III) ions. - Highlights: • Six Ln–Ag polymers have been synthesized and characterized. • The distortion of coordination geometry of Ag(I) ion affect structure framework. • Introduction of Ag(I) cause wonderful changes to the NIR

  11. A pseudo-spectral method for the simulation of poro-elastic seismic wave propagation in 2D polar coordinates using domain decomposition

    SciTech Connect

    Sidler, Rolf; Carcione, José M.; Holliger, Klaus

    2013-02-15

    We present a novel numerical approach for the comprehensive, flexible, and accurate simulation of poro-elastic wave propagation in 2D polar coordinates. An important application of this method and its extensions will be the modeling of complex seismic wave phenomena in fluid-filled boreholes, which represents a major, and as of yet largely unresolved, computational problem in exploration geophysics. In view of this, we consider a numerical mesh, which can be arbitrarily heterogeneous, consisting of two or more concentric rings representing the fluid in the center and the surrounding porous medium. The spatial discretization is based on a Chebyshev expansion in the radial direction and a Fourier expansion in the azimuthal direction and a Runge–Kutta integration scheme for the time evolution. A domain decomposition method is used to match the fluid–solid boundary conditions based on the method of characteristics. This multi-domain approach allows for significant reductions of the number of grid points in the azimuthal direction for the inner grid domain and thus for corresponding increases of the time step and enhancements of computational efficiency. The viability and accuracy of the proposed method has been rigorously tested and verified through comparisons with analytical solutions as well as with the results obtained with a corresponding, previously published, and independently benchmarked solution for 2D Cartesian coordinates. Finally, the proposed numerical solution also satisfies the reciprocity theorem, which indicates that the inherent singularity associated with the origin of the polar coordinate system is adequately handled.

  12. Anomalous nanoinclusion effects of 2D MoS2 and WS2 nanosheets on the mechanical stiffness of polymer nanocomposites

    NASA Astrophysics Data System (ADS)

    Kim, Sung-Kon; Wie, Jeong Jae; Mahmood, Qasim; Park, Ho Seok

    2014-06-01

    Polymer inorganic nanosheet composites hold great promise in enhancing their physical and mechanical properties by increasing the interfacial area. Herein, we demonstrate the nanoinclusion effects of two-dimensional (2D) molybdenum disulfide (MoS2) and tungsten disulfide (WS2) nanosheets on the mechanical properties of the poly(vinyl alcohol) (PVA) polymer. At very small amounts of nanosheets (0.9 wt% for MoS2 and 2.0 wt% for WS2), nanocomposite films exhibit up to 65% improved mechanical properties than the neat PVA film because of strong non-covalent polymer-filler interactions by means of large contact area induced by the 2D geometry of nanosheets. As demonstrated by the decrease in the crystallinity of PVA and the increase in the glass transition temperature, 2D MoS2 is a more attractive filler than 2D WS2 in terms of reinforcing mechanical properties of PVA. These findings fit well with a modified Halpin-Tsai (H-T) model including a nanoscale interfacial layer that can support the observed reinforcements with extremely small 2D filler loadings. This study highlights the strong interplay between the polymer and inorganic nanosheets which plays an important role in greatly improving the mechanical stability of nanocomposites.Polymer inorganic nanosheet composites hold great promise in enhancing their physical and mechanical properties by increasing the interfacial area. Herein, we demonstrate the nanoinclusion effects of two-dimensional (2D) molybdenum disulfide (MoS2) and tungsten disulfide (WS2) nanosheets on the mechanical properties of the poly(vinyl alcohol) (PVA) polymer. At very small amounts of nanosheets (0.9 wt% for MoS2 and 2.0 wt% for WS2), nanocomposite films exhibit up to 65% improved mechanical properties than the neat PVA film because of strong non-covalent polymer-filler interactions by means of large contact area induced by the 2D geometry of nanosheets. As demonstrated by the decrease in the crystallinity of PVA and the increase in the glass

  13. 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.

  14. 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.

  15. 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.

  16. Assembly of 4-, 6- and 8-connected Cd(II) pseudo-polymorphic coordination polymers: Synthesis, solvent-dependent structural variation and properties

    SciTech Connect

    Li, Zhao-Hao; Xue, Li-Ping; Miao, Shao-Bin; Zhao, Bang-Tun

    2016-08-15

    The reaction of Cd(NO{sub 3}){sub 2}·4H{sub 2}O, 2,5-thiophenedicarboxylic acid (H{sub 2}tdc) 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 [Cd{sub 2}(CO{sub 2}){sub 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. - Graphical abstract: Key Topic. Different solvent systems modulated three Cd(II) pseudo-polymorphic coordination polymers based on thiophene-2,5-dicarboxylate and 1,2-bis(imidazol-1′-yl)methane mixed ligands. Display Omitted - Highlights: • Three solvent-dependent Cd(II) pseudo-polymorphic coordination polymers have been synthesized. • Structural variation from 4-connected 2D layer, 6-connected 2-fold interpenetrated 3D net to 8-connected 3D net. • All complexes emit blue luminescence.

  17. Tension-Compression Fatigue Behavior of 2D and 3D Polymer Matrix Composites at Elevated Temperature

    DTIC Science & Technology

    2015-09-21

    performance in elevated temperature environments. High- temperature polymer matrix composites (HTPMCs) are being considered for such applications . However...the polymer matrix in most HTPMCs cannot operate at temperatures required for many aerospace structural applications . Continuous research seeks to...temperature polymer matrix composites (HTPMCs) applications , other polyimide resins replacement are being researched and developed due to the carcinogenic

  18. One-dimensional alignment of strong Lewis acid sites in a porous coordination polymer.

    PubMed

    Kajiwara, Takashi; Higuchi, Masakazu; Yuasa, Akihiro; Higashimura, Hideyuki; Kitagawa, Susumu

    2013-11-18

    A new lanthanoid porous coordination polymer, La-BTTc (BTTc = benzene-1,3,5-tris(2-thiophene-5-carboxylate)), was synthesized and structurally characterized to have densely aligned one-dimensional open metal sites, which were found to act as strong Lewis acid sites after the removal of the coordinated solvent.

  19. Synthesis and structural characterization of a single-crystal to single-crystal transformable coordination polymer.

    PubMed

    Tian, Yuyang; Allan, Phoebe K; Renouf, Catherine L; He, Xiang; McCormick, Laura J; Morris, Russell E

    2014-01-28

    A single-crystal to single-crystal transformable coordination polymer compound was hydrothermally synthesized. The structural rearrangement is induced by selecting a ligand that contains both strong and weaker coordinating groups. Both hydrated and dehydrated structures were determined by single crystal X-ray analysis.

  20. 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.

  1. Structural diversity in two-dimensional coordination polymers constructed from simple building-blocks; a rare example of coordination polymer polymorphs structurally characterised from multiple crystals.

    PubMed

    Barnett, Sarah A; Blake, Alexander J; Champness, Neil R; Wilson, Claire

    2005-12-21

    A family of two-dimensional coordination polymers formed from the reaction of Cd(NO(3))(2) with pyrazine or pyrimidine is reported, including rare examples of polymorphic coordination polymers which crystallise as multiple crystals. Six coordination polymers have been structurally characterised, four for pyrazine and two for pyrimidine-based systems, all of which form two-dimensional arrays utilising pyrazine/pyrimidine bridging, in some instances in combination with nitrate bridging. The compounds form either 4(4) grids (1,3,4,5), or in one instance, a 6(3) herringbone sheet structure (2). In the case of 3, two polymorphs have been identified, 3a and 3b, in which the three-dimensional arrangements of the coordination polymers differ only in the relative ordering of adjacent two-dimensional sheets. It was found that these two polymorphs crystallise in a simultaneous fashion such that each crystal studied was found to contain regions of both polymorphs and was believed to be a multiple crystal. Assessment of the phase purity of the product from the reaction of Cd(NO(3))(2) with either pyrazine or pyrimidine indicates that compounds 1and 5 are not formed when the products are formed by rapid precipitation but only when using slow-diffusion methods. It is also apparent that in almost all instances more than one product is formed from a given reaction thereby illustrating the complexity of coordination polymer formation even when using simple building-blocks. For the crystal engineer this complexity is perhaps best illustrated by the simultaneous formation of 3a and 3b where no chemical interactions differentiate the two polymorphs, presenting a seemingly insurmountable complexity in the engineering of these systems.

  2. Tellurium-containing polymer micelles: competitive-ligand-regulated coordination responsive systems.

    PubMed

    Cao, Wei; Gu, Yuwei; Meineck, Myriam; Li, Tianyu; Xu, Huaping

    2014-04-02

    Nanomaterials capable of achieving tunable cargo release kinetics are of significance in a fundamental sense and various biological or medical applications. We report a competitive coordination system based on a novel tellurium-containing polymer and its ligand-regulated release manners. Tellurium was introduced to water-soluble polymers for the first time as drug delivery vehicles. The coordination chemistry between platinum and tellurium was designed to enable the load of platinum-based drugs. Through the competitive coordination of biomolecules, the drugs could be released in a controlled manner. Furthermore, the release kinetics could be modulated by the competitive ligands involved due to their different coordination ability. This tellurium-containing polymer may enrich the family of delivery systems and provide a new platform for future biomedical nanotechnologies.

  3. From achiral ligands to chiral coordination polymers: spontaneous resolution, weak ferromagnetism, and topological ferrimagnetism.

    PubMed

    Gao, En-Qing; Yue, Yan-Feng; Bai, Shi-Qiang; He, Zheng; Yan, Chun-Hua

    2004-02-11

    Using the achiral diazine ligands bearing two bidentate pyridylimino groups as sources of conformational chirality, five azido-bridged coordination polymers are prepared and characterized crystallographically and magnetically. The chirality of the molecular units is induced by the coordination of the diazine ligands in a twisted chiral conformation. The use of L(1) (1,4-bis(2-pyridyl)-1-amino-2,3-diaza-1,3-butadiene) and L(2) (1,4-bis(2-pyridyl)-1,4-diamino-2,3-diaza-1,3-butadiene) induces spontaneous resolution, yielding conglomerates of chiral compounds [Mn(3)(L(1))(2)(N(3))(6)](n) (1) and [Mn(2)(L(2))(2)(N(3))(3)](n)(ClO(4))(n).nH(2)O (2), respectively, where triangular (1) or double helical (2) chiral units are connected into homochiral one-dimensional (1D) chains via single end-to-end (EE) azido bridges. The chains are stacked via hydrogen bonds in a homochiral fashion to yield chiral crystals. When L(3) (2,5-bis(2-pyridyl)-3,4-diaza-2,4-hexadiene) is employed, a partial spontaneous resolution occurs, where binuclear chiral units are interlinked into fish-scale-like homochiral two-dimensional (2D) layers via single EE azido bridges. The layers are stacked in a heterochiral or homochiral fashion to yield simultaneously a racemic compound, [Mn(2)(L(3))(N(3))(4)](n) (3a), and a conglomerate, [Mn(2)(L(3))(N(3))(4)](n).nMeOH (3b). On the other hand, the ligand without amino and methyl substituents (L(4), 1,4-bis(2-pyridyl)-2,3-diaza-1,3-butadiene) does not induce spontaneous resolution. The resulting compound, [Mn(2)(L(4))(N(3))(4)](n) (4), consists of centrosymmetric 2D layers with alternating single diazine, single EE azido, and double end-on (EO) azido bridges, where the chirality is destroyed by the centrosymmetric double EO bridges. These compounds exhibit very different magnetic behaviors. In particular, 1 behaves as a metamagnet built of homometallic ferrimagnetic chains with a unique "fused-triangles" topology, 2 behaves as a 1D antiferromagnet with

  4. 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

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

    SciTech Connect

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

    2016-03-15

    A new one-dimensional (1D) coordination polymer, [Zn(4,4′-bpy)(H{sub 2}O){sub 4}](ADC)·4H{sub 2}O (1) (4,4′-bpy=4,4′-bipyridine and H{sub 2}ADC=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. - Graphical abstract: A new 1D coordination polymer as catalyst for the degradation of Bismarck brown aqueous solution. - Highlights: • A 1D coordination polymer has been synthesized at room temperature. • The prepared compound was utilized for color removal of Bismarck brown dye. • Good catalytic activity and stability in the dye decolorization has been found.

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

    SciTech Connect

    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

    2016-03-15

    Three cadmium coordination polymers, [Cd(bismip)]{sub n} (1), {[Cd(bismip)(phen)]·H_2O}{sub n} (2) and {[Cd_2(bismip)_2(4,4′-bipy)]·2H_2O}{sub n} (3) (H{sub 2}bismip=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 [Cd{sub 4}(bismip){sub 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 (4·8{sup 2})(4{sup 2}·8{sup 4}) 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. - Graphical abstract: Three cadmium coordination polymers with different architectures based on 5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid have been prepared. Their photoluminescent properties were also investigated. - Highlights: • Three new Cd(II) Cps were synthesized based on H{sub 2}bismip. • Compounds 1 and 3 show 3D networks and 2 exhibits a 1D chain. • Compoud 3 exhibits good catalytic activity of methylene blue photodegradation.

  7. Structure modulation of manganese coordination polymers consisting of 1,4-naphthalene dicarboxylate and 1,10-phenanthroline.

    PubMed

    Lou, Yongbing; Wang, Jingjing; Tao, Yinhua; Chen, Jinxi; Mishima, Akio; Ohba, Masaaki

    2014-06-14

    Three new manganese coordination polymers, {[Mn2(1,4-NDC)2(phen)2](H2O)}n (1), [Mn2(1,4-NDC)2(phen)(H2O)]n (2) and {[Mn4(1,4-NDC)4(phen)4](DMF)2}n (3) (1,4-H2NDC = 1,4-naphthalene dicarboxylic acid; phen = 1,10-phenanthroline; DMF = N,N-dimethylformamide), have been synthesized solvo/hydrothermally. 1,4-NDC(2-) ligands adopt different coordination modes under different solvents and concentrations which promotes different crystal structure formation. X-ray crystal structural data reveal that compounds 1, 2 and 3 crystallize in monoclinic space groups C2/c, P21/c and C2/c, respectively. Compound 1 has Mn2 dimers connected by 1,4-NDC(2-) linkers, packing into a 2D structure in a grid pattern. Compound 2 has a three-dimensional (3D) structure which is constructed by Mn2 dimers and 1,4-NDC(2-) linkers. Each MnO4N2 node of compound 3 is linked to another by 1,4-NDC(2-) ligands to form a two-dimensional (2D) structure. Variable-temperature magnetic susceptibilities of compounds 1-3 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions.

  8. 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.

  9. Three Mn(II) coordination polymers with a bispyridyl-based quinolinate ligand: the anion-controlled tunable structural and magnetic properties.

    PubMed

    Yuan, Guozan; Shan, Weilong; Liu, Bin; Rong, Lulu; Zhang, Liyan; Zhang, Hui; Wei, Xianwen

    2014-07-07

    Three new Mn(ii) coordination polymers, namely [Mn3L6·2H2O] (), [MnL2] (), and [MnL2·2H2O] (), were prepared by solvothermal reactions of Mn(ii) salts with a bispyridyl-based quinolinate ligand. All complexes were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray crystallography. Single crystal X-ray studies show that these coordination polymers exhibit a structural diversification due to the different counteranions (OAc(-), Cl(-), and NO3(-)). Complex has a 2D supramolecular structure with a cyclic tetramer Mn3L6 secondary building unit. Complex possesses a rhombohedral grid network containing a type of meso-helical chain (P + M) constructed via the metal-ligand coordination interaction. Complex features a 3D non-porous structure based on the arrangement of 2D grids. Magnetic susceptibility measurements indicate that the three Mn(ii) polymers show disparate magnetic properties due to their different supramolecular structures.

  10. Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence.

    PubMed

    Zhou, Xiaoyan; Guo, Yanling; Shi, Zhaohua; Song, Xueqin; Tang, Xiaoliang; Hu, Xiong; Zhu, Zhentong; Li, Pengxuan; Liu, Weisheng

    2012-02-14

    Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2 : 3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.

  11. 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.

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

    SciTech Connect

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

    2016-07-15

    Two zinc coordination polymers {[Zn_2(TPPBDA)(oba)_2]·DMF·1.5H_2O}{sub n} (1), {[Zn(TPPBDA)_1_/_2(tpdc)]·DMF}{sub 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 [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. 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. - Graphical abstract: Two zinc coordination polymers have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. In addition, the photoluminescent properties for TPPBDA ligand under different status and coordination polymers have been investigated in detail. Display Omitted - Highlights: • Two Zn coordination polymers based on mononuclear or dinuclear cluster units have been synthesized. • Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. • Compound 2 is a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. • The photoluminescent properties for TPPBDA with different state and two coordination polymers have been investigated.

  13. Porphyrin-Cored Polymer Nanoparticles: Macromolecular Models for Heme Iron Coordination.

    PubMed

    Rodriguez, Kyle J; Hanlon, Ashley M; Lyon, Christopher K; Cole, Justin P; Tuten, Bryan T; Tooley, Christian A; Berda, Erik B; Pazicni, Samuel

    2016-10-03

    Porphyrin-cored polymer nanoparticles (PCPNs) were synthesized and characterized to investigate their utility as heme protein models. Created using collapsible heme-centered star polymers containing photodimerizable anthracene units, these systems afford model heme cofactors buried within hydrophobic, macromolecular environments. Spectroscopic interrogations demonstrate that PCPNs display redox and ligand-binding reactivity similar to that of native systems and thus are potential candidates for modeling biological heme iron coordination.

  14. 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.

  15. 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

  16. Design and construction of diverse structures of coordination polymers: Photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Wu, Yu; Lu, Lu; Feng, Jianshen; Li, Yulong; Sun, Yanchun; Ma, Aiqing

    2017-01-01

    The reaction of Cu(NO3)2·3H2O/Ni(NO3)2·6H2O with 4‧-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2‧:6‧,4‧‧-terpyridine (H2dbp) gave [Cu0.5(Hdbp)]n (1) and [Ni(dbp)(H2O)]n (2), while the reactions of Co(NO3)2·6H2O with H2dbp in the presence of 4,4‧-bipy and 2,2‧-bpy generated [Co(dbp)(4,4‧-bipy)]n (3) and {[Co(dbp)(2,2‧-bipy)]n·H2O} (4), respectively (4,4‧-bipy=4.4‧-pyridine and 2,2‧-bipy=2,2‧-bipyridine). X-Ray single-crystal analyses reveal that 1 contains a 1D double chain. 2 possesses a 3D architecture with (4.620.83)2 topology that is interpenetrated with each other to form a 2-fold network. In 3, the 2D [Co(dbp)]n sheets are pillared by 4,4‧-bpy to form a 3D framework with 1D open channel. Compound 4 consists of a 1D ladder-like chain. The results showed that the structural diversity of the coordination polymers resulted from the different geometries of metal ions and effect of assistant ligands. Furthermore, the photocatalytic properties of 1-4 for degradation of the methyl violet (MV) have been examined.

  17. 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.

  18. An unprecedented extended architecture constructed from a 2-D interpenetrating cationic coordination framework templated by SiW 12O 404- anion

    NASA Astrophysics Data System (ADS)

    Wang, Xiuli; Lin, Hongyan; Bi, Yanfeng; Chen, Baokuan; Liu, Guocheng

    2008-03-01

    A novel inorganic-organic hybrid compound based on polyoxometalates (POMs) and organic ligand formulated as [Cu 2( bpp) 4(H 2O) 2](SiW 12O 40)˜6H 2O ( 1) [ bpp=1,3-bis(4-pyridyl)propane], was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction analysis, IR, TG, and cyclic voltammetry. Crystal data for 1: Orthorhombic, Pbcn, a=23.0085(19) Å, b=14.6379(12) Å, c=23.6226(19) Å, V=7956.0(11) Å 3, Z=4, Dc=3.315 g cm -3, and R(final)=0.0826. X-ray diffraction study reveals that compound 1 was the first interpenetrating network of 2-D metal-organic cationic coordination framework [Cu 2( bpp) 4(H 2O) 2] n4n+, in which Keggin-type anions SiW 12O 404- has been used as a non-coordinating anionic template. The electrochemical property of 1-bulk modified carbon paste electrode ( 1-CPE) has been studied, and the results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite in 1 M H 2SO 4 aqueous solution.

  19. Coordination-Driven Self-Assembly of a 2D Graphite-Like Framework Constructed from High-Nuclear Ce10 Cluster Encapsulated Polyoxotungstates.

    PubMed

    Ma, Pengtao; Wan, Rong; Wang, Yueyan; Hu, Feng; Zhang, Dongdi; Niu, Jingyang; Wang, Jingping

    2016-01-19

    It is challenging to explore and prepare high-nuclear lanthanide (Ln) cluster-encapsulated polyoxometalates (POMs). Herein, we fabricate an unprecedented Ce10-cluster-embedded polyoxotungstate (POT) (TMA)14H2[Ce(III)(H2O)6]{[Ce(IV)7Ce(III)3O6(OH)6(CO3)(H2O)11][(P2W16O59)]3}·41H2O (1) (TMA = tetramethyleneamine) by coordination-driven self-assembly strategy, which contains the largest Ce cluster [Ce(IV)7Ce(III)3O6(OH)6(CO3)(H2O)11] (Ce10) in all the Ln-containing POM chemistry to date. Self-assembly of the in situ dilacunary [P2W16O59](12-) fragments and mixed Ce(3+) and Ce(4+) ions by means of coordination-driven force results in a novel 2D graphite-like framework constructed from mixed-valent cerium(III/IV) cluster {Ce10} encapsulated poly(POT) units and Ce(3+) ions. The most remarkable feature is that the skeleton of the centrosymmetric Ce10-cluster-embedded POT trimer contains three dilacunary [P2W16O59](12-) fragments trapping a novel {Ce10} cluster via 18 terminal-oxo and three μ4-oxo atoms.

  20. Dialkylthio Substitution: An Effective Method to Modulate the Molecular Energy Levels of 2D-BDT Photovoltaic Polymers.

    PubMed

    Yao, Huifeng; Zhang, Hao; Ye, Long; Zhao, Wenchao; Zhang, Shaoqing; Hou, Jianhui

    2016-02-17

    Dialkylthio-substituted thienyl-benzodithiophene (BDT-DST) was designed and synthesized as a building block to modulate the molecular levels of the conjugated polymers, and three copolymers named PDST-BDD, PDST-TT and PDST-DPP were prepared and applied in polymer solar cells (PSCs). Theoretical calculations and electrochemical cyclic voltammetry (CV) measurement suggested that the dialkylthio group could decrease the molecular energy levels of the resulting polymers distinctly. The open-circuit voltage (VOC) of PSC devices based on PDST-BDD, PDST-TT, and PDST-DPP are as high as 1.0, 0.98, and 0.88 V, respectively, which are ∼0.15 V higher than those of the corresponding alky-substituted analogues. Moreover, the influence of the dialkylthio group on the absorption spectra, crystalline properties, hole mobilities, and blend morphologies of the polymers was also investigated. The results indicate that the dialkythio substitution is an effective method to modulate the molecular energy levels and that the BDT-DST unit has potential for constructing high-efficiency photovoltaic polymers.

  1. Zn(II) coordination polymers with flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

    SciTech Connect

    Li, Lin; Liu, Chong-Bo; Yang, Gao-Shan; Xiong, Zhi-Qiang; Liu, Hong; Wen, Hui-Liang

    2015-11-15

    Hydrothermal reactions of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) and zinc ions in the presence of N-donor ancillary ligands afford four novel coordination polymers, namely, [Zn{sub 2}(μ{sub 2}-OH)(μ{sub 4}-O){sub 0.5}(L)]·0.5H{sub 2}O (1), [Zn(L)(2,2′-bipy)(H{sub 2}O)] (2), [Zn{sub 3}(L){sub 3}(phen){sub 2}]·H{sub 2}O (3) and [Zn{sub 2}(L){sub 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 [Zn{sub 4}(µ{sub 4}-O)(µ{sub 2}-OH){sub 2}]{sup 4+} clusters, and exhibits a novel (3,8)-connected topological net with the Schläfli symbol of {3·4·5}{sub 2}{3"4·4"4·5"2·6"6·7"1"0·8"2}, 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 {4"4·6"2} 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 {4"4·6"2} square structure with left- and right-handed helical chains. Moreover, the luminescent properties of 1–4 have been investigated. - Graphical abstract: Four new Zn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent properties have been investigated. - Highlights: • Four novel Zn(II) coordination polymers with V-shaped ligand were characterized. • Complexes 1–4 show diverse intriguing helical characters. • Fluorescence properties of complexes 1–4 were investigated.

  2. 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.

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

    PubMed Central

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

    2015-01-01

    In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design1. 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 may inform the design of soft materials for use in complex mechanical environments. PMID:26322715

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

    PubMed

    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.

  5. 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.

  6. Organic Solar Cells Based on a 2D Benzo[1,2-b:4,5-b']difuran-Conjugated Polymer with High-Power Conversion Efficiency.

    PubMed

    Huo, Lijun; Liu, Tao; Fan, Bingbing; Zhao, Zhiyuan; Sun, Xiaobo; Wei, Donghui; Yu, Mingming; Liu, Yunqi; Sun, Yanming

    2015-11-18

    A novel 2D benzodifuran (BDF)-based copolymer (PBDF-T1) is synthesized. Polymer solar cells fabricated with PBDF-T1 show high power conversion efficiency of 9.43% and fill factor of 77.4%, which is higher than the performance of its benzothiophene (BDT) counterpart (PBDT-T1). These results provide important progress for BDF-based copolymers and demonstrate that BDF-based copolymers can be competitive with the well-studied BDT counterparts via molecular structure design and device optimization.

  7. Assembly of three new POM-based Ag(I) coordination polymers with antibacterial and photocatalytic properties

    SciTech Connect

    Lu, Xin-Xin; Luo, Yu-Hui; Lu, Chen; Chen, Xin; Zhang, Hong

    2015-12-15

    Three new silver coordination polymers, namely, {Ag_3(bpy)_6[PW_1_2O_4_0]} (1), {Ag_5(H_2biim)_2(Hbiim-NO_2)_2[PW_1_2O_4_0]} (2), {Ag_7(pytz)_4[PW_1_2O_4_0]} (3) (bpy=2,2′-bipyridine, H{sub 2}biim=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. - Highlights: • Three new silver coordination polymers have been synthesized under hydrothermal condition. • Due to different coordination modes of rigid N-donor ligands, structures of the title compounds vary from 0D to 3D frameworks. • It is noteworthy that nitration happens to compound 2 during the hydrothermal condition, which is quite rare. • In addition, these compounds exhibit efficiency of photocatalytic decomposition of dyes and antibacterial activities.

  8. Host-Guest Engineering of Coordination Polymers for Highly Tunable Luminophores Based on Charge Transfer Emissions.

    PubMed

    Zhao, Bei; Li, Na; Wang, Xi; Chang, Ze; Bu, Xian-He

    2017-01-25

    Aiming at the targeted construction of coordination polymer luminophores, the engineering of host-guest architectures with charge transfer based emissions is performed by utilizing the interactions between the electron-deficient 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (tpt) and electron-rich polycyclic aromatic hydrocarbons (PAHs) motifs as acceptors and donors, respectively. Through guest modulation of a prototype coordination polymer [Cd(tpt)(1,4-pda)(H2O)2]·(tpt)·(H2O)2 (1) (1,4-H2pda = 1,4-phenylenediacetic acid), a series of coordination polymers with different PAHs as guests, [Cd2(tpt)2(1,4-pda)2]·guest (2-5) (guest = triphenylene for 2, pyrene for 3, coronene for 4, and perylene for 5), are successfully fabricated. Distinct from 1, coordination polymers 2-5 reveal unique bilayer structures with PAHs interlayer and good stability, owing to the enhanced stacking interactions between tpt motifs and PAH guests. Moreover, their emissions cover a wide range of wavelength due to the effective guest to host charge transfer interactions between donor and acceptor motifs. Their readily tunable host-guest charge transfer based emissions make them good candidates as potential luminophores.

  9. Reversible stimulus-responsive Cu(I) iodide pyridine coordination polymer.

    PubMed

    Amo-Ochoa, P; Hassanein, K; Gómez-García, C J; Benmansour, S; Perles, J; Castillo, O; Martínez, J I; Ocón, P; Zamora, F

    2015-10-01

    We present a structurally flexible copper-iodide-pyridine-based coordination polymer showing drastic variations in its electrical conductivity driven by temperature and sorption of acetic acid molecules. The dramatic effect on the electrical conductivity enables the fabrication of a simple and robust device for gas detection. X-ray diffraction studies and DFT calculations allow the rationalisation of these observations.

  10. Enhanced bistability by guest inclusion in Fe(II) spin crossover porous coordination polymers.

    PubMed

    Muñoz Lara, Francisco J; Gaspar, Ana B; Aravena, Daniel; Ruiz, Eliseo; Muñoz, M Carmen; Ohba, Masaaki; Ohtani, Ryo; Kitagawa, Susumu; Real, José A

    2012-05-16

    Inclusion of thiourea guest molecules in the tridimensional spin crossover porous coordination polymers {[Fe(pyrazine)[M(CN)(4)]} (M = Pd, Pt) leads to novel clathrates exhibiting unprecedented large thermal hysteresis loops of ca. 60 K wide centered near room temperature.

  11. 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

    2016-03-07

    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.

  12. A rational route to SCM materials based on a 1-D cobalt selenocyanato coordination polymer.

    PubMed

    Boeckmann, Jan; Näther, Christian

    2011-07-07

    Thermal annealing of a discrete complex with terminal SeCN anions and monodentate coligands enforces the formation of a 1D cobalt selenocyanato coordination polymer that shows slow relaxation of the magnetization. Therefore, this approach offers a rational route to 1D materials that might show single chain magnetic behaviour.

  13. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

    PubMed

    Abraham, Anuji; Crull, George

    2014-10-06

    A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

  14. 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.

  15. 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%).

  16. 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.

  17. 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.

  18. New reversible crystal-to-crystal conversion of a mixed-ligand lead(II) coordination polymer by de- and rehydration.

    PubMed

    Sadeghzadeh, Homa; Morsali, Ali

    2009-12-07

    A reversible crystal-to-crystal transformation of a new 2D lead(II) coordination polymer with the ligand 4-pyridinecarboxylic acid (4-Hpyc), [Pb(4-pyc)(Br)(H(2)O)](n) (1) to [Pb(4-pyc)(Br)](n) (2) by de- and rehydration, has been observed, and the structures of 1 and 2 have been determined by single-crystal X-ray diffraction. The thermal stabilities of compounds 1 and 2 were studied by thermal gravimetric and differential thermal analyses. Powder X-ray diffraction experiments showed that the structural transformation occurs in the batch powder samples and leads to monophasic products.

  19. 2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion.

    PubMed

    Kang, Keehoon; Watanabe, Shun; Broch, Katharina; Sepe, Alessandro; Brown, Adam; Nasrallah, Iyad; Nikolka, Mark; Fei, Zhuping; Heeney, Martin; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Sirringhaus, Henning

    2016-08-01

    Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

  20. Systematic design and research on a series of cadmium coordination polymers assembled due to tetracarboxylate ligands

    SciTech Connect

    Lü, Lei; Mu, Bao; Li, Chang-Xia; Huang, Ru-Dan

    2016-02-15

    A series of metal-organic frameworks (MOFs) have been prepared by tetracarboxylate ligands and Cd(II) ions under the hydrothermal or solvothermal conditions with the formulas of {[Cd_2(L_1)(H_2O)_4]·H_2O}{sub n} (1), {[(CH_3)_2NH_2]_2[Cd(L_1)]}{sub n} (2), [Cd(L{sub 2}){sub 0.5}(H{sub 2}O)]{sub n} (3), {[(CH_3)_2NH_2]_2 [Cd(L_2)]·2DMF}{sub n} (4), [Cd(L{sub 3}){sub 0.5}(H{sub 2}O)]{sub n} (5), {[Cd(L_3)_0_._5(H_2O)]·CH_3OH}{sub n} (6), {[(CH_3)_2NH_2]_2[Cd_3(L_4)_2]}{sub n} (7) (H{sub 4}L{sub 1}=[1,1′:4′,1″-terphenyl]-2,2″,5,5″-tetracarboxylic acid; H{sub 4}L{sub 2}=[1,1′:4′,1″-terphenyl]-2′,4,4″,5′-tetracarboxylic acid; H{sub 4}L{sub 3}=[1,1′:3′,1″-terphenyl]-2′,3,3″,5′-tetracarboxylic acid; H{sub 4}L{sub 4}=[1,1′:4′,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid), which are characterized by single-crystal X-ray diffraction, elemental analyses, IR, TGA and PXRD. Complex 1 exhibits a three-dimensional (3D) supramolecular framework based on two-dimensional (2D) coordination networks. Complexes 2 and 4 possess 3D framework based on the 1D right-handed helix channels. Complexes 3 and 7 are a 3D architecture containing two different channels. Isostructural complexes 5 and 6 display 3D framework. The different synthetic methods and coordination modes of the tetracarboxylates ligands have effect on formation of various MOFs. Moreover, the luminescent properties and N{sub 2} adsorption behaviors have been reported. - Graphical abstract: A series of cadmium(II) high-dimensional coordination polymers constructed from four different kinds of tetracarboxylate ligands have been successfully prepared under hydrothermal or solvothermal conditions. The effect of solvents, the coordination modes of the tetracarboxylates and positions of carboxylate groups on the architectures of complexes 1–7 have been investigated in detail. The luminescent properties of the part of complexes, N{sub 2} adsorption behaviors of complexes 2, 4–7 have

  1. 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.

  2. Porous coordination polymer with flexibility imparted by coordinatively changeable lithium ions on the pore surface.

    PubMed

    Xie, Lin-Hua; Lin, Jian-Bin; Liu, Xiao-Min; Wang, Yu; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming

    2010-02-01

    Solvothermal reactions of equimolar zinc acetate, lithium acetate, and 1,3,5-benzenetricarboxylic acid (H(3)btc) in different mixed solvents yielded isostructural three-dimensional frameworks [LiZn(btc)(cG)].lG [cG and lG denote coordinated and lattice guests, respectively; cG = (nmp)(0.5)(H(2)O)(0.5), lG = (EtOH)(0.5) (1a); cG = H(2)O, lG = EtOH (1b); nmp = N-methyl-2-pyrrolidone] with one-dimensional channels occupied by guest molecules and solvent-coordinated, extrusive Li(+) ions. Thermogravimetry analyses and powder X-ray diffraction measurements revealed that both 1a and 1b can lose all lattice and coordinated guests to form a desolvated phase [LiZn(btc)] (MCF-27, 1) and almost retains the original framework structure. Gas adsorption measurements on 1 confirmed its permanent porosity but suggested a structural transformation from 1a/1b to 1. It is noteworthy that only 1a can undergo a single-crystal to single-crystal (SCSC) transformation into 1 upon desolvation. The crystal structure of 1 revealed that the Li(+) ions were retracted into the channel walls via complementary coordination to the carboxylate oxygen atoms in the framework rather than being exposed on the pore surface. Single-crystal X-ray diffraction analyses were also performed for N(2)- and CO(2)-loaded samples of 1, revealing that the framework remained unchanged when the gases were adsorbed. Although the gas molecules could not be modeled, the residue electrons inside the channels demonstrated that the retracted Li(+) ions still behave as the primary interacting site for CO(2) molecules. Nevertheless, solvent molecules such as H(2)O can readily compete with the framework oxygen atom to retrieve the extrusive Li(+) ions, accompanying the reverse structural transformation, i.e., from 1 to 1a/1b.

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

    SciTech Connect

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

    2016-07-15

    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)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=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 (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The

  4. pySeismicFMM: Python based travel time calculation in regular 2D and 3D grids in Cartesian and geographic coordinates using Fast Marching Method

    NASA Astrophysics Data System (ADS)

    Polkowski, Marcin

    2016-04-01

    Seismic wave travel time calculation is the most common numerical operation in seismology. The most efficient is travel time calculation in 1D velocity model - for given source, receiver depths and angular distance time is calculated within fraction of a second. Unfortunately, in most cases 1D is not enough to encounter differentiating local and regional structures. Whenever possible travel time through 3D velocity model has to be calculated. It can be achieved using ray calculation or time propagation in space. While single ray path calculation is quick it is complicated to find the ray path that connects source with the receiver. Time propagation in space using Fast Marching Method seems more efficient in most cases, especially when there are multiple receivers. In this presentation a Python module pySeismicFMM is presented - simple and very efficient tool for calculating travel time from sources to receivers. Calculation requires regular 2D or 3D velocity grid either in Cartesian or geographic coordinates. On desktop class computer calculation speed is 200k grid cells per second. Calculation has to be performed once for every source location and provides travel time to all receivers. pySeismicFMM is free and open source. Development of this tool is a part of authors PhD thesis. National Science Centre Poland provided financial support for this work via NCN grant DEC-2011/02/A/ST10/00284.

  5. Enantioselective synthesis of a chiral coordination polymer with circularly polarized visible laser.

    PubMed

    Wu, Shu-Ting; Cai, Zhen-Wen; Ye, Qiao-Yan; Weng, Chen-Hao; Huang, Xi-He; Hu, Xiao-Lin; Huang, Chang-Cang; Zhuang, Nai-Feng

    2014-11-17

    Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL-responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL-induced enantioselective synthesis. By irradiation with either left-handed or right-handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left-handed CPL resulted in crystals with a left-handed helical structure, and right-handed CPL led to crystals with a right-handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.

  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. Transport and deposition of polymer-modified Fe0 nanoparticles in 2-D heterogeneous porous media: effects of particle concentration, Fe0 content, and coatings.

    PubMed

    Phenrat, Tanapon; Cihan, Abdullah; Kim, Hye-Jin; Mital, Menka; Illangasekare, Tissa; Lowry, Gregory V

    2010-12-01

    Concentrated suspensions of polymer-modified Fe(0) nanoparticles (NZVI) are injected into heterogeneous porous media for groundwater remediation. This study evaluated the effect of porous media heterogeneity and the dispersion properties including particle concentration, Fe(0) content, and adsorbed polymer mass and layer thickness which are expected to affect the delivery and emplacement of NZVI in heterogeneous porous media in a two-dimensional (2-D) cell. Heterogeneity in hydraulic conductivity had a significant impact on the deposition of NZVI. Polymer modified NZVI followed preferential flow paths and deposited in the regions where fluid shear is insufficient to prevent NZVI agglomeration and deposition. NZVI transported in heterogeneous porous media better at low particle concentration (0.3 g/L) than at high particle concentrations (3 and 6 g/L) due to greater particle agglomeration at high concentration. High Fe(0) content decreased transport during injection due to agglomeration promoted by magnetic attraction. NZVI with a flat adsorbed polymeric layer (thickness ∼30 nm) could not be transported effectively due to pore clogging and deposition near the inlet, while NZVI with a more extended adsorbed layer thickness (i.e., ∼70 nm) were mobile in porous media. This study indicates the importance of characterizing porous media heterogeneity and NZVI dispersion properties as part of the design of a robust delivery strategy for NZVI in the subsurface.

  8. 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.

  9. 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.

  10. Molecular tectonics: generation and structural studies on 1- and 2D coordination networks based on a meta-cyclophane in 1,3-alternate conformation bearing four pyrazolyl units and cobalt, zinc and copper cations.

    PubMed

    Ehrhart, Jérôme; Planeix, Jean-Marc; Kyritsakas-Gruber, Nathalie; Hosseini, Mir Wais

    2009-08-28

    The combination of a [1111] metacyclophane blocked in 1,3-alternate conformation and bearing four pyrazolyl coordinating units with MX(2) (M = Co, Zn and X = Cl or Br) leads to the formation of crystals formed by packing of 2D coordination networks. In the case of CuBr(2), the formation of a 1D network was observed. Structural studies by X-ray diffraction methods on single crystals were performed on all cases reported.

  11. Hydrothermal synthesis of two copper helical coordination polymers with acentric three-dimensional framework constructing from mixed pyridine carboxylates

    SciTech Connect

    Zhang Shuai; Cao Yanning; Zhang Hanhui Chai Xiaochuan; Chen Yiping

    2008-03-15

    Two copper helical coordination polymers, [Cu(2-pc)(3-pc)]{sub n}1 and [Cu(2-pc)(4-pc)]{sub n}2 (2-pc=2-pyridine carboxylate, 3-pc=3-pyridine carboxylate, 4-pc=4-pyridine carboxylate) have been hydrothermally synthesized directly from pyridine carboxylic acids and copper nitrate. The crystal structure were determined by single-crystal X-ray diffraction with the following data: compound 1, orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=6.591(3) A, b=8.692(5) A, c=20.548(9) A, V=1177.2(9) A{sup 3}, Z=4; compound 2, orthorhombic, Pna2{sub 1}, a=21.160(10) A, b=9.095(5) A, c=6.401(3) A, V=1231.9(11) A{sup 3}, Z=4. The acentric three-dimensional (3D) framework of 1 is constructed from right-handed helical Cu(2-pc) chains and left-handed Cu(3-pc) helices. As for 2, Cu(2-pc) helical chains, in which left- and right-handed helices are coexisting, and Cu(4-pc) zigzag chains combined together to form acentric 3D architecture of 2 as well. Additionally, besides general spectral characterization, we first introduce generalized 2D correlation spectroscopy to explore the coordination polymers and ascertain the stretching vibration location of carboxylate groups of compounds 1 and 2. -- Abstract: Two copper helical coordination polymers, [Cu(2-pc)(3-pc)]{sub n}1 and [Cu(2-pc)(4-pc)]{sub n}2 have been obtained by hydrothermal synthesis. Both two compounds crystallized in non-centrosymmetric space groups, P2{sub 1}2{sub 1}2{sub 1} and Pna2{sub 1}, respectively. The 3D framework of 1 is constructed from right-handed helical Cu(2-pc) chains and left-handed Cu(3-pc) helices. As for 2, Cu(2-pc) helical chains, in which left- and right-handed helices are coexisting, and Cu(4-pc) zigzag chains combined together to form 3D architecture of 2 as well.

  12. 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.

  13. Magnetite nanoparticle-supported coordination polymer nanofibers: synthesis and catalytic application in Suzuki-Miyaura coupling.

    PubMed

    Liao, Yetong; He, Lisi; Huang, Jing; Zhang, Jianyong; Zhuang, Lin; Shen, Hui; Su, Cheng-Yong

    2010-08-01

    Functional nanoscale coordination polymers are receiving growing scientific interest because of their potential applications in many domains. In this paper, we demonstrated that a nanofibrous networked metal-organic gel (G1-MNPs) was formed by simply mixing 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris(N-(pyridin-3-ylmethyl)benzamide) (L) and Pd(COD)(NO(3))(2) in CHCl(3)-MeOH with a Pd/L molar ratio of 1:1 in the presence of magnetite nanoparticle (MNPs). The self-assembly behavior of nanofibers was not significantly effected by the introduction of magnetite nanoparticles. The xerogel of G1-MNPs was superparamagnetic and showed catalytic activity in Suzuki-Miyaura C-C coupling reactions. The Pd(II) xerogel could be magnetically isolated and recycled with a permanent magnet. It represents a novel strategy to introduce nanoparticles into functional coordination polymers for multifunctional materials.

  14. 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.

  15. Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

    NASA Astrophysics Data System (ADS)

    Luo, Qianqian; Han, Ying; Lin, Hechun; Zhang, Yuanyuan; Duan, Chungang; Peng, Hui

    2017-03-01

    One dimensional coordination polymer Gd[(SO4)(NO3)(C2H6SO)2] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO42- ions to generate a 1-D chain, and all oxygen atoms in SO42- groups are connected to three nearest Gd atoms in μ3:η1:η1:η2 fashion. Gd, S and N from SO42- and NO3- are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with -ΔSm=28.8 J Kg-1 K-1 for ΔH=7 T.

  16. Zinc coordination polymers containing substituted isophthalate ligands and fragments from in situ hydrolysis of 4-pyridylisonicotinamide

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Hydrothermal treatment of zinc nitrate, a 5-substituted isophthalic acid, and 4-pyridylisonicotinamide (4-pina) resulted in crystalline coordination polymers that incorporated different fragments formed by in situ hydrolysis of the 4-pina precursor. These materials were characterized by single crystal X-ray diffraction. In the case of {[4-ampyrH]2[Zn(hip)2]·H2O}n (1, 4-ampyrH = 4-aminopyridinium, hip = 5-hydroxyisophthalate), anionic [Zn(hip)2]n2n- (4,4) grid layers co-crystallize with protonated 4-ampyr cations. Using 5-nitroisophthalic acid (H2nip), [Zn7(isonic)4(OH)6(nip)2]n (2, isonic = isonicotinate) was formed. This material manifests [Zn7(OH)6]n cationic inorganic chain motifs linked by isonic and nip ligands into a non-interpenetrated 3-D coordination polymer network with pcu topology. Luminescent behavior is attributed to intra-ligand molecular orbital transitions.

  17. 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.

  18. Sequestering aromatic molecules with a spin-crossover Fe(II) microporous coordination polymer.

    PubMed

    Muñoz-Lara, Francisco J; Gaspar, Ana B; Muñoz, M Carmen; Arai, Masashi; Kitagawa, Susumu; Ohba, Masaaki; Real, José Antonio

    2012-06-25

    All in a spin: A series of three-dimensional porous coordination polymer {Fe(dpe)[Pt(CN)(4)]}⋅G (dpe = 1,2-di(4-pyridyl)ethylene; G = phenazine, anthracene, or naphthalene) exhibiting spin crossover and host-guest functions is reported. The magnetic properties of the framework are very sensitive to the chemical nature (aromatic or hydroxilic solvents) and the size of the included guest molecules.

  19. Enhanced photoelectrochemical biosensing performances for graphene (2D) - Titanium dioxide nanowire (1D) heterojunction polymer conductive nanosponges.

    PubMed

    Muthuchamy, N; Lee, K-P; Gopalan, A-I

    2017-03-15

    In this work, an efficient photoelectrochemical (PEC) biosensing platform has been designed and developed based on graphene (G) through modifying it into an electroconductive polymer nanosponge (EPNS) and with the incorporation of titanium dioxide nanowires (TiO2 NW) (designated as TiO2 (G) NW@EPNS). Functioning as an efficient immobilization matrix for immobilization of the enzyme Cytochrome C (Cyt C), TiO2 (G) NW@EPNS delivers features for an efficient PEC biosensor, such as fast kinetics of direct electron transfer (DET) to the electrode and effective separation of photogenerated holes and electrons. TiO2 (G) NW@EPNS exhibited DET to the electrode with a highly heterogeneous electron transfer rate constant of 6.29±0.002s(-1). The existence of TiO2, G and EPNS in conjunction facilitates DET between the electrode surface and the protein. The fabricated PEC nitrite ion (NO2(-)) biosensor showed superior analytical performances such as wide linear range (0.5-9000µM), lowest detection limit (0.225mM) and excellent specificity for NO2(-) in the presence other interferences at a very low bias potential (-0.11V). This study opens up the feasibility of fabricating a PEC biosensor for any analyte using a matrix comprising of G and a photoactive material and EPNS, because these components synergistically contribute to effective immobilization of on enzyme, DET to the electrode and simple read-out under the light.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

    Two new 3D bismuth containing coordination polymers are reported along with their single crystal structures and SHG properties. Compound 1: Bi2O2(pydc) (pydc=pyridine-2, 5-dicarboxylate), crystallizes in the monoclinic, polar space group, P21 (a=9.6479(9) Å, b=4.2349(4) Å, c=11.9615(11) Å, β=109.587(1)°), which contains Bi2O2 chains that are connected into a 3D structure via the pydc ligands. Compound 2: Bi4Na4(1R3S-cam)8(EtOH)3.1(H2O)3.4 (1R3S cam=1R3S-camphoric acid) crystallizes in the monoclinic, polar space group, P21 (a=19.0855(7) Å, b=13.7706(5) Å, c=19.2429(7) Å, β=90.701(1)°) 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 Bi3+, a synthetic approach that resulted in polar, non-centrosymmetric, 3D metal-organic coordination polymer.

  2. 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.

  3. 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

  4. Synthesis of Highly Porous Coordination Polymers with Open Metal Sites for Enhanced Gas Uptake and Separation.

    PubMed

    Song, Kyung Seob; Kim, Daeok; Polychronopoulou, Kyriaki; Coskun, Ali

    2016-10-12

    Metal-containing amorphous microporous polymers are an emerging class of functional porous materials in which the surface properties and functions of polymers are dictated by the nature of the metal ions incorporated into the framework. In an effort to introduce coordinatively unsaturated metal sites into the porous polymers, we demonstrate herein an aqueous-phase synthesis of porous coordination polymers (PCPs) incorporating bis(o-diiminobenzosemiquinonato)-Cu(II) or -Ni(II) bridges by simply reacting hexaminotriptycene with CuSO4·5H2O [Cu(II)-PCP] or NiCl2·6H2O [Ni(II)-PCP] in H2O. The resulting polymers showed surface areas of up to 489 m(2) g(-1) along with a narrow pore size distribution. The presence of open metal sites significantly improved the gas affinity of these frameworks, leading to an exceptional isosteric heat of adsorption of 10.3 kJ·mol(-1) for H2 at zero coverage. The high affinities of Cu(II)- and Ni(II)-PCPs toward CO2 prompted us to investigate the removal of CO2 from natural and landfill gas conditions. We found that the higher affinity of Cu(II)-PCP compared to that of Ni(II)-PCP not only allowed for the tuning of the affinity of CO2 molecules toward the sorbent, but also led to an exceptional CO2/CH4 selectivity of 35.1 for landfill gas and 20.7 for natural gas at 298 K. These high selectivities were further verified by breakthrough measurements under the simulated natural and landfill gas conditions, in which both Cu(II)- and Ni(II)-PCPs showed complete removal of CO2. These results clearly demonstrate the promising attributes of metal-containing porous polymers for gas storage and separation applications.

  5. Metal ions directed assembly of two coordination polymers based on an organic phosphonate anion and a multidentate N-donor ligand

    NASA Astrophysics Data System (ADS)

    Kan, Wei-Qiu; Xu, Ji-Ming; Wen, Shi-Zheng; Yang, Lin

    2017-01-01

    Two new coordination polymers [Cd(4,4‧-tmbpt)(HL)(H2O)] (1) and [Cu(4,4‧-tmbpt)(HL)]·H2O (2) (H3L = 2‧-carboxybiphenyl-4-ylmethylphosphonic and 4,4‧-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole) have been synthesized hydrothermally. The two compounds have the same metal to ligand ratio, but different metal ions. As a result, the two compounds display different 2D layer structures, which is mainly caused by the different coordination numbers of the different metal ions. The effects of the metal ions on the structures, the optical band gaps and photoluminescent and photocatalytic properties of the compounds have been studied.

  6. 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.

  7. Ultrasonic assisted synthesis of two new coordination polymers and their applications as precursors for preparation of nano-materials.

    PubMed

    Masoomi, Mohammad Yaser; Morsali, Ali; Junk, Peter C; Wang, Jun

    2017-01-01

    Two new isostructural coordination polymers, [Zn3(Oba)4][Me2NH2)2]·6DMF·3H2O (1) and [Cd3(Oba)4][Me2NH2)2]·2DMF·2H2O (2), were synthesized using the nonlinear dicarboxylate ligand, 4,4'-oxybis(benzoic acid) (H2oba) and characterized by IR spectroscopy and single-crystal X-ray crystallography. Single-crystal X-ray data show that 1 and 2 are two-dimensional coordination polymers that can be extended to three-dimensional supramolecular networks by CH…O interactions. These two new coordination polymers were also sonochemically synthesized while sonication time and power of irradiation influencing size and morphology of nano-structured compounds were also studied. Moreover, calcination of these coordination polymers creates ZnO and CdO nanostructures.

  8. Coordination polymer based on Cu(II), Co(II) and 4,4'-bipyridine-2,6,2',6'-tetracarboxylate: synthesis, structure and adsorption properties.

    PubMed

    Zhao, Zhou; He, Xiang; Zhao, Yongmei; Shao, Min; Zhu, Shourong

    2009-04-21

    4,4'-Bipyridine-2,6,2',6'-tetracarboxylic acid H4L.3H2O, () and its copper(II) and cobalt (II) coordination polymers [Cu2L(H2O)4]2n () and {[Co(H2O)6].[Co3L2(H2O)2].10H2O}3n () have been hydrothermally synthesized. Compound packs into a crystal via H-bonds. Complex is a 2D coordination grid, in which Cu is in an elongated octahedral constructed by a mer-geometry pyridyl-2,6-dicarboxylate, one bridging carboxylate oxygen and two water molecules. The L4- is central symmetrical. Each pyridyl-2,6-dicarboxylate chelete to Cu(II) and one carboxylate bridge Cu(II) ions in a 1,1-fashion. The 2D coordination polymer links to adjacent layers via H-bonds. Complex is a metal-organic framework with 11.6x10.5 A rectangular channels. All Co(II) ions are located in an octahedral coordination environment. The rectangular channels are composed of Co2+-L4- walls and the walls are linked through carboxylate oxygen atoms and Co(II) ions. Co(H2O)6(2+) as counter ions fill in porous channel. The removal of water molecules from at 210 degrees C or higher affords the porous material [Co4L2]n, which can adsorb 16 (36%) methanol or 9 (32%) ethanol in the vapour phase. The porosity of is higher than reported 4,4'-bipyridine-2,6,2',6'- tetracarboxylate complexes. The framework of remains but the crystallinity is lost upon removal of the H2O molecules. The dehydrated framework of partially recovery crystallinity after it adsorbs H2O, CH3OH and C2H5OH. The methanol in the framework can be replaced by H2O reversibly.

  9. Design and its limitations in the construction of bi- and poly-nuclear coordination complexes and coordination polymers (aka MOFs): a personal view.

    PubMed

    Robson, R

    2008-10-14

    This article, presented from a personal point of view, is concerned with the design of ligands intended to give specifically either binuclear or tetranuclear metal complexes or coordination polymers. No attempt is made to provide a comprehensive coverage of these topics, the focus being mainly upon results from our laboratory. Some emphasis is placed upon aspects of the historical development of the deliberate construction of coordination polymers (aka MOFs)--materials promising useful applications, the study of which continues to expand exponentially. Some of our recent research is described in which the carbonate ion and the tetracyanoquinodimethane dianion are used as bridging ligands to generate targeted coordination polymers. It is intended that Dalton Perspectives be easily comprehensible to non-specialists in the field; an average second year university chemistry student should be easily able to understand the present contribution.

  10. Halochromic coordination polymers based on a triarylmethane dye for reversible detection of acids.

    PubMed

    Zavakhina, Marina S; Yushina, Irina V; Samsonenko, Denis G; Dybtsev, Danil N; Fedin, Vladimir P; Argent, Stephen P; Blake, Alexander J; Schröder, Martin

    2017-01-03

    Chromeazurol B (Na2HL) is a pH-sensitive (halochromic) dye based on a hydroxytriarylmethane core and two carboxylate functional groups, which makes it suitable for the synthesis of coordination polymers. Two new coordination polymers [NaZn4(H2O)3(L)3]·3THF·3H2O (1) and [Zn3(H2O)3(μ2-OH2)(μ3-OH)(HL)2(H2L)]·2THF·3H2O (2) incorporating Chromeazurol B linkers have been prepared and characterised. The structure of 1 comprises pentanuclear heterometallic {Zn4Na} nodes linked by six L(3-) anions to give a layered structure with a honeycomb topology. 2 crystallizes as a double-chain ribbon (ladder) structure with two types of metal node: a mononuclear Zn(ii) cation and tetranuclear {Zn(ii)}4 cluster. Chromeazurol B anions link each tetranuclear cluster to four individual Zn(ii) cations and each Zn(ii) cation with four tetranuclear clusters. Both compounds show pH-sensitivity in water solution which can be observed visually, giving the first example of a halochromic coordination polymer. The halochromic properties of 1 towards HCl vapors were systematically investigated. As-synthesized violet-grey 1 reversibly changes color from orange to pink in the presence of vapors of 2 M and 7 M HCl, respectively. The coordination of the Chromeazurol B anion at each color stage was examined by diffuse reflectance spectroscopy and FT-IR measurements. The remarkable stability of 1 to acid and the observed reversible and reproducible color changes provide a new design for multifunctional sensor materials.

  11. Facile fabrication and adsorption property of a nano/microporous coordination polymer with controllable size and morphology.

    PubMed

    Liu, Qing; Jin, Li-Na; Sun, Wei-Yin

    2012-09-11

    A porous coordination polymer [Cu(3)(btc)(2)] with controllable size and morphology from nanocube to microoctahedron was readily synthesized in an ethanol-water mixture at room temperature by adjusting the concentration of the surfactant and the polymer shows size- and morphology-dependent sorption properties.

  12. Synthesis, spectral characterization and thermal aspects of coordination polymers of some transition metal ions with adipoyl bis(isonicotinoylhydrazone)

    NASA Astrophysics Data System (ADS)

    Haque, Mahejabeen Azizul; Paliwal, L. J.

    2017-04-01

    A series of metal coordination polymers of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), obtained by the reaction of metal acetate with newly synthesized adipoyl bis(isonicotinoylhydrazone) (ADBI) have been investigated. The ligand has been characterized by 1H NMR, 13C NMR, FTIR, and ESI mass spectra. Structural and spectroscopic characterization of the coordination polymers have been carried out using elemental analysis, XRD, SEM, infrared and diffused reflectance spectra, magnetic susceptibility measurements and thermogravimetric analytical techniques. Each metal ion is coordinated to the ligand through oxygen of carbonyl group and the nitrogen of azomethine group of ligand forming a stable 5-membered heterocyclic ring. The synthesized ligand coordinates in an octadentate manner. Magnetic and diffused reflectance spectral studies reveal octahedral geometry of Co(II), Cu(II), Fe(II) and Ni(II) coordination polymers and tetrahedral geometry of Mn(II) and Zn(II) coordination polymers. The thermal stability and decomposition steps of all coordination polymers have been studied using TG, DTG and DTA techniques. Moreover, the kinetic parameters such as activation energy (Ea*), order of reaction (n), Arrhenius factor (A), change in entropy (ΔS*), change in enthalpy (ΔH*) and free energy change (ΔG*) were evaluated at each stage of decomposition curve using Coats-Redfern method.

  13. 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.

  14. Synthesis and structural characterization of one- and two-dimensional coordination polymers based on platinum-silver metallic backbones.

    PubMed

    Liu, Fenghui; Chen, Wanzhi; Wang, Daqi

    2006-06-28

    Seven Pt-Ag coordination polymers [Pt(NH3)2(NHCO(t)Bu)2Ag(H2O)](ClO4) (1), [Pt2(dap)2(NHCO(t)Bu)4Ag2(NO3)(ClO4)] (dap = 1,2-diaminopropane, 2), [Pt2(en)2(NHCO(t)Bu)4Ag2(m-C6H4(CO2)2)].3H2O (en = ethylenediamine, 3), [Pt2(NH3)2(NHCO(t)Bu)2Ag2(p-C6H4(CO2)2)].2H2O (4), [Pt3(en)3(NHCO(t)Bu)6Ag2(p-C6H4(CO2)2)(1.5)].6H2O (5), [Pt(NH3)2(NHCO(t)Bu)4Ag(4-C5H4NCO2)2].10H2O (6), and [Pt2(en)2(NHCO(t)Bu)4Ag2(4-C5H4NCO2)](ClO4) (7) were synthesized from the corresponding [Pt(RNH2)2(NHCO(t)Bu)2] and Ag salts, respectively, and their structures were determined by X-ray crystallography. The Pt and Ag units aggregate into one-dimensional chains based on Pt-Ag backbones. Compounds 1, 2, and 6 possess an extended zigzag Pt-Ag chain motif, and the metallic chains arrange in a parallel fashion into layered structures. Compounds 3-5, and 7 form 2-D brick wall sheets due to the coordination of the bifunctional anions to the Ag+ ions of the neighboring chains. These polymers are constructed based on the Pt-Ag interactions and the coordination of amidate oxygen atoms to Ag ions. There are three kinds of short Pt-Ag bonds observed in the structures of these compounds. The Pt-Ag metallic backbone is formed by the stacking unsupported Pt-Ag bonds, the amidate doubly bridged Pt-Ag bonds, and the amidate singly bridged Pt-Ag bonds. In the chains, the Pt-Ag bond distances are quite short, and appear in the range of 2.78-2.97 A, which are comparable to known Pt-Ag dative bonds.

  15. Preparation and characterization of lanthanide-azo-dye coordination polymers and polymer thin films via layer-by-layer depositions.

    PubMed

    Han, Li-Wei; Lü, Jian; Liu, Tian-Fu; Gao, Shui-Ying; Cao, Rong

    2010-12-07

    A series of tartrazine-lanthanide dye compounds has been synthesized and characterized. Structural studies reveal that the light rare-earth elements La, Ce, Pr and Nd form coordination compounds with tartrazine ligands in a 1:1 ratio and result in 1-D 'fish-bone' chain-like structures having uncoordinated organosulfonate groups on each side of the chain. However, reactions of tartrazine and heavy rare-earth elements Ho, Er, Tm and Yb, in the presence of auxiliary 1,10-phenanthroline, give new 1-D coordination polymers in which uncoordinated organosulfonate groups are located on the same side of the chains. The tartrazine ligands display similar but slightly different coordination modes in both types of structures and the 1,10-phenanthroline plays a vital role in the formation of heavy rare-earth dye compounds. Based on the knowledge of their structures, the light rare-earth dye compounds were utilized to assemble with positively-charged PEI into multilayer thin films by means of layer-by-layer depositions. The as-synthesized thin films showed enhanced stability and consistency on solid surfaces.

  16. Two novel two-dimensional copper(II) coordination polymers with 1-(4-aminobenzyl)-1,2,4-triazole: Synthesis, crystal structure, magnetic characterization and absorption of anion pollutants

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Wu, Xiang Xia; Guo, Jian-Hua; Huo, Jian-Zhong; Ding, Bin

    2017-01-01

    In this work a flexible multi-dentate 1-(4-aminobenzyl)-1,2,4-triazole (abtz) ligand has been employed, two novel triazole-Cu(II) coordination polymers {[Cu(abtz)2(Br)2]·(H2O)2}n (1) and {[Cu(abtz)2]·(SiF6)·(H2O)2}n (2) have been isolated under solvo-thermal conditions. 1 is a 2D neutral CuII coordination polymer while 2 is 2D cation micro-porous CuII coordination polymer with the channel dimensionalities of 11.852(1) Å × 11.852(1) Å (metal-metal distances). Variable-temperature magnetic susceptibility data of 1 and 2 have been recorded in the 2-300 K temperature range indicating weak anti-ferromagnetic interactions. Further absorption properties of anion pollutants for 2 also have been investigated. 2 presents the novel example of cationic triazole-copper(II) coordination framework for effectively capturing anion pollutants Cr2O72- in the water solutions and selectively capturing Congo Red in the methanol solutions.

  17. A facile route for preparing a mesoporous palladium coordination polymer as a recyclable heterogeneous catalyst.

    PubMed

    Zhang, Siyong; Liu, Qinghua; Shen, Ming; Hu, Bingwen; Chen, Qun; Li, Hexing; Amoureux, Jean-Paul

    2012-04-21

    To overcome the separation difficulty of the palladium-based homogeneous catalyst, the palladium complex can be anchored on various supports such as silica, polymers and nanoparticles. For the same purpose, we describe a general and facile method to immobilize palladium bis(phosphine) complexes on the basis of the technique widely used for metal-organic framework (MOF) synthesis, yielding a mesoporous coordination polymer palladium-CP1. Although palladium complexes are generally not stable enough to allow further manipulation, we succeeded in preparation of a palladium coordination polymer without by-product Pd clusters or nanoparticles. The fresh palladium-CP1 catalyst exhibits a yield close to 55% for tolane at room temperature and 24 h in Sonogashira coupling of iodobenzene and phenylacetylene, as compared with a yield of 89% for its homogeneous counterpart [Pd(PPh(3))(2)Cl(2)]. Furthermore, this catalyst is stable enough to be reused more than four times with no Pd and Zn leaching. Therefore this new immobilization method offers great promise for the produce of recyclable palladium heterogeneous catalysts with higher activity and higher thermal and chemical stability in the future.

  18. 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.

  19. 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.

  20. Porous coordination polymers of diverse topologies based on a twisted tetrapyridylbiaryl: application as nucleophilic catalysts for acetylation of phenols.

    PubMed

    Seth, Saona; Venugopalan, Paloth; Moorthy, Jarugu Narasimha

    2015-01-26

    Porous coordination polymers (CPs) with partially uncoordinated pyridyl rings based on rationally designed polypyridyl linkers are appealing from the point of view of their application as nucleophilic catalysts. A D2d -symmetric tetradentate organic linker L, that is, 2,2',6,6'-tetramethoxy-3,3',5,5'-tetrakis(4-pyridyl)biphenyl, was designed and synthesized for metal-assisted self-assembly aimed at porous CPs. Depending on the nature of the metal ion and the counter anion, the ligand L is found to function as a 3- or 4-connecting building block leading to porous CPs of diverse topologies. The reaction of L with Zn(NO3 )2 and Cd(NO3 )2 yields porous 2 D CPs of "fes" topology, in which the tetrapyridyl linker L serves as a 3-connecting unit with its free pyridyl rings well exposed into the pores. The functional utility of these porous CPs containing uncoordinated pyridyl rings is demonstrated by employing them as efficient heterogeneous nucleophilic catalysts for acetylation of a number of phenols with varying electronic properties and reactivities.

  1. New oxalate-propagated layered Mn2+/Fe2+-4,4‧-sulfoyldiphthalhydrazidate coordination polymers

    NASA Astrophysics Data System (ADS)

    Jin, Juan; Yan, Wen-Fu; Yang, Qing-Feng; Yu, Xiao-Yang; Sun, Li-Xiang; Xu, Ji-Qing; Chen, Zi-Ao; Li, Chuan-Zhao

    2017-01-01

    Based on the hydrothermal in situ acylation reaction of 4,4‧-sulfoyldiphthalic anhydride (sdpha) with N2H4ṡH2O, two isostructural oxalate-propagated Mn2+/Fe2+-diacylhydrazidate coordination polymers, [M3(sdpth)2(ox)(H2O)2]ṡ2H2O (M2+ = Mn2+1, Fe2+2; sdpth = 4,4‧-sulfoyldiphthalhydrazidate, ox = oxalate), were obtained and characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. In both compounds, ox ligands act as the second linkers, extending the metal-diacylhydrazidate chains into a 2-D layer. Via Nsbnd H⋯O interactions, compounds 1 and 2 self-assemble into 3-D supramolecular networks. The magnetic analyses indicate that there are antiferromagnetic interactions between magnetic centers in compounds 1 and 2. The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution.

  2. Four new coordination polymers based on carboxyphenyl-substituted dipyrazinylpyridine ligand: Syntheses, structures, magnetic and luminescence properties

    NASA Astrophysics Data System (ADS)

    Yuan, Fei; Zhang, Lu; Hu, Huai-Ming; Bai, Chao; Xue, Ganglin

    2017-01-01

    Four new coordination polymers, namely, [Co(L)2]n (1) and [Co(L)(tp)0.5]n·nH2O (2), [Zn(L)2]n·0.5nH2O (3) and [Zn(L)(suc)0.5]n·nH2O (4) (HL = 4-(3-carboxyphenyl)-2,6-di(pyrazinyl)pyridine, H2tp = benzene-1,4-dicarboxylic acid, H2suc = succinic acid), were constructed by changing metal ion and introducing auxiliary ligand under hydrothermal condition. X-ray single diffraction studies reveal that compounds 1 and 3 have similar structures and crystallized in the monoclinic system with P21/c space group, which show infinite zigzag chains and are further extended into a 2D supramolecular layer by inter-molecular hydrogen bonds. Compounds 2 and 4 display infinite ladder chains and are further extended into a 3D supramolecular network by inter-molecular hydrogen bonds. Additionally, magnetic and photoluminescence properties of 1-4 have been investigated.

  3. 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

    2015-04-09

    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.

  4. Hydrothermal synthesis of copper coordination polymers based on molybdates: Chemistry issues

    NASA Astrophysics Data System (ADS)

    Pavani, K.; Ramanan, A.; Whittingham, M. S.

    2006-08-01

    Crystal engineering of metal organic coordination polymers or metal organic frameworks have been attracting unprecedented efforts in the past few years due to potential applications in the area of catalysis, gas separation and storage. Hydrothermal synthesis is a popular soft chemical route employed by a number of researchers to grow suitable single crystals for unambiguous structural characterization. The structural diversity of the various solid frameworks is attributed to the choice of metal, its ability to exist in multiple oxidation states exhibiting different coordination geometry and multidentate nature of organic ligands. Polyoxomolybdate is another interesting class of inorganic materials that are potential catalysts. A contemporary theme is to develop porous solids combining the acidic properties of oligomeric molybdates integrated with first-row transition metal ions that can form coordination polymers with suitable multidentate ligands. A bottleneck to this problem is to develop reliable synthetic protocols that can produce reproducible materials with designed structural characteristics. In this paper, we present our results on the formation of self-assembled metal organic hybrid solids from acidified aqueous molybdate solution containing cupric ions and one of the multidentate organic ligands (pyrazine, 2-pyrazine carboxylic acid or isonicotinic acid). We propose a molecular mechanism to rationalize the formation of solids.

  5. 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

  6. Coordination Architectures of energetic Cd (II) coordination polymers constructed by the bifunctional substituted-tetrazole-carboxylate ligands

    NASA Astrophysics Data System (ADS)

    Shen, Lei; Bai, Yu; Min, Yu-Ting; Jia, Tian-Tian; Wu, Qi; Wang, Jing; Geng, Fei; Cheng, Hong-Jian; Zhu, Dun-Ru; Yang, Jie; Yang, Gao-Wen

    2016-12-01

    Three different tetrazole-carboxylate ligands, monotetrazole-carboxylate H2tza (H2tza=1,5-tetrazole-diacetic acid), Hpztza (Hpztza=5-(2-pyrazinyl)tetrazole-2(1-methyl)acetic acid), ditetrazole-carboxylate H2tzpha (H2tzpha=1,3-di(tetrazole-5-yl)benzene-N2,N2‧-diacetic acid) have been chosen to react with CdCl2·6H2O, resulting in the formation of three new compounds [Cd2(tza)2] (1), [Cd(pztza)2] (2) and [Cd(tzpha)(CH3OH)2] (3). The coordinate sites of the three ligands are major influenced by the different substituted group of tetrazole ring. These compounds have been characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 displays a complex 3D structure; compound 2 shows a 3D network and compound 3 features a 2D layer network. Furthermore, the luminescence properties investigated at room temperature in the solid state showed excellent ligand-centered luminescence. The obvious enhancement in luminescence makes these compounds potential materials for optical use. The differential scanning calorimetry (DSC) and thermogravimetric-differential thermogravimetric (TG-DTG) analyses were applied to evaluate the thermal decomposition behavior of such compounds, showing that compounds 2 and 3 can be used as potential energetic materials. The relevant thermodynamic parameters ΔH, ΔS and ΔG were calculated as well.

  7. Water-Resistant and Transparent Plastic Films from Functionalizable Organic Polymers: Coordination Polymers as Templates for Solid-State [2+2]-Photopolymerization.

    PubMed

    Garai, Mousumi; Biradha, Kumar

    2017-01-05

    An organic polymer containing cyclobutanes and amides as backbones and pyridyl groups as sidearms was synthesized by single-crystal-to-single-crystal (SCSC) [2+2]-photopolymerization in the coordination polymers (CPs) of diene. The diene molecule was photo-inactive in its crystals and formed a triply intertwined 1D-helical CP with Cd(NO3 )2 and Cu(NO3 )2 salts. The 1D-CP was transformed into a coordination polymer of organic polymers containing threefold interpenetrated 3D-networks of CdSO4 topology through a [2+2]-reaction in SCSC manner upon irradiation. The organic polymer was separated from its CPs and found to have an unusually high degree of polymerization for this type of reaction. Furthermore, the organic polymer was amenable for N-alkylation reactions such as methylation, propylation, and decylation. The formate salts of the organic polymer and the methylated polymer were shown to form plastic films with a combination of properties such as high transparency, tensile strengths, gas permeability, thermal stability, water-resistance, and resistance to other organic solvents. The methylated polymer was also able to capture chromate ions and anionic dyes from aqueous solutions.

  8. Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces.

    PubMed

    Yan, Xuzhou; Li, Shijun; Pollock, James Bryant; Cook, Timothy R; Chen, Jianzhuang; Zhang, Yanyan; Ji, Xiaofan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2013-09-24

    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.

  9. A flexible pro-porous coordination polymer: non-conventional synthesis and separation properties towards CO(2)/CH(4) mixtures.

    PubMed

    Barea, Elisa; Tagliabue, Giulia; Wang, Wen-Guo; Pérez-Mendoza, Manuel; Mendez-Liñan, Laura; López-Garzon, Francisco J; Galli, Simona; Masciocchi, Norberto; Navarro, Jorge A R

    2010-01-18

    The novel coordination polymers [Cu(Hoxonic)(H(2)O)](n) (1) and [Cu(Hoxonic)(bpy)(0.5)](n)1.5 n H(2)O (2 subsetH(2)O) (H(3)oxonic: 4,6-dihydroxy-1,3,5-triazine-2-carboxylic acid; bpy: 4,4'-bipyridine) have been isolated and structurally characterised by ab initio X-ray powder diffraction. The dense phase 1 contains 1D zig-zag chains in which Hoxonic dianions bridge square-pyramidal copper(II) ions, apically coordinated by water molecules. On the contrary, 2 subsetH(2)O, prepared by solution and solventless methods, is based on 2D layers of octahedral copper(II) ions bridged by Hoxonic ligands, further pillared by bpy spacers. The resulting pro-porous 3D network possesses small hydrated cavities. The reactivity, thermal, magnetic and adsorptive properties of these materials have been investigated. Notably, the adsorption studies on 2 show that this material possesses unusual adsorption behaviour. Indeed, guest uptake is facilitated by increasing the thermal energy of both the guest and the framework. Thus, neither N(2) at 77 K nor CO(2) at 195 K are incorporated, and CH(4) is only minimally adsorbed at 273 K and high pressures (0.5 mmol g(-1) at 2500 kPa). By contrast, CO(2) is readily incorporated at 273 K (up to 2.5 mmol g(-1) at 2500 kPa). The selectivity of 2 towards CO(2) over CH(4) has been investigated by means of variable-temperature zero coverage adsorption experiments and measurement of breakthrough curves of CO(2)/CH(4) mixtures. The results show the highly selective incorporation of CO(2) in 2, which can be rationalised on the basis of the framework flexibility and polar nature of its voids.

  10. Copper(II)-Thymine Coordination Polymer Nanoribbons as Potential Oligonucleotide Nanocarriers.

    PubMed

    Vegas, Verónica G; Lorca, Romina; Latorre, Ana; Hassanein, Khaled; Gómez-García, Carlos J; Castillo, Oscar; Somoza, Álvaro; Zamora, Félix; Amo-Ochoa, Pilar

    2017-01-19

    The direct reaction between copper nitrate, thymine-1-acetic acid, and 4,4'-bipyridine in water leads to the formation of a blue colloid comprising uniform crystalline nanoribbons (length >1 μm; width ca. 150-185 nm; diameter ca. 15-60 nm) of a coordination polymer. The polymer displays a thymine-based structure freely available for supramolecular interactions. These nanostructures show significant selective interaction with single-stranded oligonucleotides based on adenine. Remarkably, they present low cell toxicity in three cell lines-despite the copper(II) content-and can be used as nanocarriers of oligonucleotides. These results suggest the potential of these types of nanostructures in several biological applications.

  11. Two new coordination polymers based on tartaric acid ligand: Syntheses, crystal structure and thermal stability

    NASA Astrophysics Data System (ADS)

    Chen, Fei-Yan; Lan, You-Zhao; Han, Min-Min; Feng, Yun-Long

    2016-09-01

    Two new coordination polymers [Cd3(D-Tar)3]n ( 1) and [Pb( meso-Tar)]n ( 2) (H2 Tar = tartaric acid) have been synthesized by hydrothermal reaction and characterized by single crystal X-ray diffraction analysis and IR spectra. 1 crystallizes in the C2221 chiral space group and shows a 3D (4,4)-connected net with the (4.6.84)4(4.62.82.10)(4.62.83)(4.63.82)(4.63.82)4(4.85)2 topology. 2 possesses a 3D (4,4)-connected net with the (43.62.8) topology. In addition, the thermogravimetric analyses (TGA) results for polymers are discussed.

  12. Facile preparation and dual catalytic activity of copper(I)-metallosalen coordination polymers.

    PubMed

    Hou, Yun-Long; Li, Sheng-Xia; Sun, Raymond Wai-Yin; Liu, Xin-Yuan; Weng Ng, Seik; Li, Dan

    2015-10-21

    Three copper(i)-metallosalen coordination polymers (CPs), {[Ni(II)(SalImCy)]2(Cu(I)CN)9}n (1), {[Cu(II)(SalImCy)]2(Cu(I)CN)9}n (2) and {[Ni(II)(SalImCy)](Cu(I)I)2·DMF}n (3) were prepared by direct combination of Ni(II)/Cu(II)(salen) motifs with [Cu(I)CN]n chains and Cu2I2 clusters via the metalloligand strategy. The mixed-valence and mixed-metal CPs could effectively catalyze both the oxidation of aromatic alcohols to ketones and aldehydes under mild conditions and photocatalytic degradation of organic dye methylene blue (MB). This work demonstrates the effective integration of transition metal catalytic Ni(II)/Cu(II)(salen) units and photoactive copper(i) species in a single solid polymer to meet the demand for catalytic materials with the dual catalytic properties.

  13. 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.

  14. 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.

  15. Two unprecedented 1D coordination polymer chains based on tetranuclear copper(II) building blocks

    SciTech Connect

    Li Gaijuan; Xing Yan Song Shuyan; Xu Ning; Liu Xianchun; Su Zhongmin

    2008-09-15

    The reaction of copper(II) sulfate with pyridine in DMF or methanol yield two unprecedented Cu(II) coordination polymers {l_brace}[Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}][{mu}-Cu(py)(DMF){sub 2}]{r_brace}{sub n}(1) and {l_brace}[Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}][{mu}-Cu(py){sub 4}]{r_brace}{sub n}(2), respectively. Single-crystal X-ray diffraction indicated that compound 1 crystallizes in the monoclinic system, space group p2(1)/n, a=14.542(5) A, b=16.359(5) A, c=18.951(5) A, {beta}=92.047(5){sup o}, V=4505(2) A{sup 3}, Z=4 while 2 is monoclinic C2/c, a=23.078(5) A, b=10.214(5) A, c=23.142(5) A, {beta}=115.471(5){sup o}, V=4925(3) A{sup 3}, Z=4. Both of the two compounds consist of tetrahedral tetranuclear [Cu{sub 4}({mu}{sub 4}-O)(py){sub 4}(SO{sub 4}){sub 4}] clusters that are bridged by pentacoordinated Cu atom for 1 or hexacoordinated Cu atoms for 2 through the sulfate oxygen to form the infinite one-dimensional polymer chains. - Graphical abstract: Two unprecedented Cu(II) coordination polymers have been prepared by using solvothermal method; they consist of tetrahedral tetranuclear clusters that are bridged by unique Cu(II) atom through the sulfate oxygen to form the infinite one-dimensional polymer chains (a) for complex 1 and (b) for complex 2.

  16. Guest-Dependent Spin-Transition Behavior of Porous Coordination Polymers.

    PubMed

    Ohtani, Ryo; Hayami, Shinya

    2017-02-16

    The host-guest composites of Hofmann-type iron(II) spin-transition (ST) porous coordination polymers incorporating guest molecules show guest-dependent ST behavior in accordance with the respective guest species, which may be a gas, solvent, halogen, or organic molecule. The guest also works as a chemical stimulant to switch the spin state of the host between high and low spin at room temperature. In this review, we discuss guest properties including size, shape, flexibility, chemical properties, and pore loading content, which impact the spin states of the host framework and the ST behavior exhibited by the host-guest composites.

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

    PubMed

    Bauer, Wolfgang; Lochenie, Charles; Weber, Birgit

    2014-02-07

    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.

  18. Soluble Metal-Nanoparticle-Decorated Porous Coordination Polymers for the Homogenization of Heterogeneous Catalysis.

    PubMed

    Huang, Yuan-Biao; Wang, Qiang; Liang, Jun; Wang, Xusheng; Cao, Rong

    2016-08-17

    Ultrasmall metal nanoparticles (MNPs) were decorated on soluble porous coordination polymers (PCPs) with high metal loadings. The solubility of the composite and the size of the MNPs can be controlled by varying the ratio of the precursors to the supports. The soluble PCPs can serve as a platform to homogenize heterogeneous MNPs catalysts, which exhibited excellent activity and recyclability in C-H activation and Suzuki reactions. This strategy combines the advantages of homogeneous and heterogeneous catalysis and may bring new inspiration to catalysis.

  19. Synthesis, crystal structure, and porosity estimation of hydrated erbium terephthalate coordination polymers.

    PubMed

    Daiguebonne, Carole; Kerbellec, Nicolas; Bernot, Kevin; Gérault, Yves; Deluzet, André; Guillou, Olivier

    2006-07-10

    The reaction of the Er3+ ion with polycarboxylate ligands in gel media leads to coordination polymers exhibiting various structural types and dimensionalities. Five Er3+/1,4-benzenedicarboxylate-based coordination polymers have been obtained in such conditions. Four out of the five are new. Their crystal structures are reported and compared herein. Compound 1, namely, Er2Ter3(H2O)6, where H2Ter symbolizes the terephthalic acid, crystallizes in the space group P1 (No. 2) with a = 7.8373(10) A, b = 9.5854(2) A, c = 10.6931(2) A, alpha = 68.7770(8) degrees, beta = 70.8710(8) degrees, and gamma = 75.3330(12) degrees. It has already been reported elsewhere. The last four compounds are new. Compound 2, namely, Er2Ter3(H2O)6 x 2 H2O, crystallizes in the space group P121/a1 (No. 14) with a = 6.7429(2) A, b = 22.4913(7) A, c = 9.6575(3) A, and beta = 91.6400(18) degrees. Compound 3, namely Er2Ter3(H2O)8 x 2 H2O crystallizes in the space group P1 (No. 2) with a = 7.5391(2) A, b = 10.0533(3) A, c = 10.4578(3) A, alpha = 87.7870(10) degrees, beta = 82.5510(11) degrees, and gamma = 86.2800(16) degrees. Compound 4, namely, Er2Ter3(H2O)6 x 2 H2O crystallizes in the space group C2/c (No. 15) with a = 38.5123(13) A, b = 11.1241(4) A, c = 7.0122(2) A, and beta = 98.634(2) degrees. Compound 5, namely, Er2Ter3(H2O)6 x H2O, crystallizes in the space group P1 (No. 2) with a = 6.8776(10) A, b = 11.0420(2) A, c = 18.5675(3) A, alpha = 84.7240(6) degrees, beta = 81.8380(6) degrees, and gamma = 84.1770(8) degrees. A computational method has also been developed to evaluate the potential porosity of the coordination polymers. This method is described and then applied to the different Er2Ter3(H2O)n coordination polymers previously described.

  20. 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.

  1. 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.

  2. Crystal-chemical role of malonate ions in the structure of coordination polymers

    NASA Astrophysics Data System (ADS)

    Serezhkin, V. N.; Medvedkov, Ya. A.; Serezhkina, L. B.; Pushkin, D. V.

    2015-06-01

    In the crystal structures of the malonate-containing compounds of d- or f-metals, the C3H2O{4/2-} anions were found to exhibit 17 topologically different types of coordination to the metal atoms A, playing the role of mono-, bi-, tri-, or tetradentate ligands and forming one to seven O-A bonds. The C-C-C bond angle in the malonate ions changed from 103° to 126° and depended linearly on the dihedral angle (φCOO) between the planes of the two carboxyl groups of the anion. At φCOO < 60°, the malonate ions in the crystal structures always form six-membered metallocycles with d- or f-metal atoms, while at φCOO > 67°, they can form only four-membered metallocycles. The factors that influence the conformation of malonate ions in the structures of coordination polymers were discussed.

  3. Lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand: thermal and optical properties.

    PubMed

    Seidel, Christiane; Lorbeer, Chantal; Cybińska, Joanna; Mudring, Anja-Verena; Ruschewitz, Uwe

    2012-04-16

    By slow diffusion of triethylamine into a solution of 2,3,5,6-tetrafluoroterephthalic acid (H2tfBDC) and the respective lanthanide salt in EtOH/DMF single crystals of seven nonporous coordination polymers, (∞)(2)[Ln(tfBDC)(NO(3))(DMF)(2)]·DMF (Ln(3+) = Ce, Pr, Nd, Sm, Dy, Er, Yb; C2/c, Z = 8) have been obtained. In the crystal structures, two-dimensional square grids are found, which are composed of binuclear lanthanide nodes connected by tfBDC(2-) as a linking ligand. The coordination sphere of each lanthanide cation is completed by a nitrate anion and two DMF molecules (CN = 9). This crystal structure is unprecedented in the crystal chemistry of coordination polymers based on nonfluorinated terephthalate (BDC(2-)) as a bridging ligand; as for tfBDC(2-), a nonplanar conformation of the ligand is energetically more favorable, whereas for BDC(2-), a planar conformation is preferred. Differential thermal analysis/thermogravimetric analysis (DTA/TGA) investigations reveal that the noncoordinating DMF molecule is released first at temperatures of 100-200 °C. Subsequent endothermal weight losses correspond to the release of the coordinating DMF molecules. Between 350 and 400 °C, a strong exothermal weight loss is found, which is probably due to a decomposition of the tfBDC(2-) ligand. The residues could not be identified. The emission spectra of the (∞)(2)[Ln(tfBDC)(NO(3))(DMF)(2)]·DMF compounds reveal intense emission in the visible region of light for Pr, Sm, and Dy with colors from orange, orange-red, to warm white.

  4. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    NASA Astrophysics Data System (ADS)

    Vlassa, Mihaela; Bende, Attila

    2015-08-01

    Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet-triplet transition was studied in details and the corresponding spin-orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  5. In situ hydrothermal synthesis of tetrazole coordination polymers with interesting physical properties.

    PubMed

    Zhao, Hong; Qu, Zhi-Rong; Ye, Heng-Yun; Xiong, Ren-Gen

    2008-01-01

    Tetrazole compounds have been studied for more than one hundred years and applied in various areas. Several years ago Sharpless and his co-workers reported an environmentally friendly process for the preparation of 5-substituted 1H-tetrazoles in water with zinc salt as catalysts. To reveal the exact role of the zinc salt in this reaction, a series of hydrothermal reactions aimed at trapping and characterizing the solid intermediates were investigated. This study allowed us to obtain a myriad interesting metal-organic coordination polymers that not only partially showed the role of the metal species in the synthesis of tetrazole compounds but also provided a class of complexes displaying interesting chemical and physical properties such as second harmonic generation (SHG), fluorescence, ferroelectric and dielectric behaviors. In this tutorial review, we will mainly focus on tetrazole coordination compounds synthesized by in situ hydrothermal methods. First, we will discuss the synthesis and crystal structures of these compounds. Their various properties will be mentioned and we will show the applications of tetrazole coordination compounds in organic synthesis. Finally, we will outline some expectations in this area of chemistry. The direct coordination chemistry of tetrazoles to metal ions and in situ synthesis of tetrazole through cycloaddition between organotin azide and organic cyano group will be not discussed in this review.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Three new coordination polymers of uranium(VI) with pyromellitic acid (H4btca) have been synthesized and structurally characterized. (ED)[(UO2)(btca)]·(DMSO)·3H2O (1) (ED=ethylenediammonium; DMSO=dimethylsulfoxide) has a lamellar structure with intercalation of ED and DMSO. (NH4)2[(UO2)6O2(OH)6(btca)]·~6H2O (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). [(UO2)2(H2O)(btca)]·4H2O (3) has a 3D network constructed by two types of 7-fold coordinated uranium polyhedron. The unique μ5-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.

  7. 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.

  8. 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.

  9. 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

    2012-09-03

    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.

  10. Electrical bistability around room temperature in an unprecedented one-dimensional coordination magnetic polymer.

    PubMed

    Amo-Ochoa, Pilar; Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martin, Avelino; Zamora, Félix

    2013-05-20

    The synthesis, crystal structure, and physical properties of an unprecedented one-dimensional (1D) coordination polymer containing [Fe2(S2C6H2Cl2)4](2-) entities bridged by dicationic [K2(μ-H2O)2(THF)4](2+) units are described. The magnetic properties show that the title compound presents pairwise Fe-Fe antiferromagnetic interactions that can be well reproduced with a S = 1/2 dimer model with an exchange coupling, J = -23 cm(-1). The electrical conductivity measurements show that the title compound is a semiconductor with an activation energy of about 290 meV and two different transitions, both with large hysteresis of about 60 and 30 K at 260-320 K and 350-380 K, respectively. These two transitions are assumed to be due to slight structural changes in the cation-anion interactions. Differential Scanning Calorimetry confirms the presence of both transitions. This compound represents the first sample of a coordination polymer showing electrical bistability.

  11. 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.

  12. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    NASA Astrophysics Data System (ADS)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-01

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox)0.5(H2O)]n·2n(H2O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H2sfpip)(ox)(H2O)4]n·2n(H2O) (Ln=Nd (8) Sm (9)), [H2ox=oxalic acid, H3sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H3sfpip resulted in two types of structures. Compounds 1-7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox2- anions as linkers to bridge the adjacent layers. Compounds 8-9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1-7 to 8-9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1-9 were also investigated.

  13. Ligand effects on the structural dimensionality and antibacterial activities of silver-based coordination polymers.

    PubMed

    Lu, Xinyi; Ye, Junwei; Sun, Yuan; Bogale, Raji Feyisa; Zhao, Limei; Tian, Peng; Ning, Guiling

    2014-07-14

    Four Ag-based coordination polymers [Ag(Bim)] (1), [Ag2(NIPH)(HBim)] (2), [Ag6(4-NPTA)(Bim)4] (3) and [Ag2(3-NPTA)(bipy)0.5(H2O)] (4) (HBim = 1H-benzimidazole, bipy = 4,4'-bipyridyl, H2NIPH = 5-nitroisophthalic acid, H2NPTA = 3-/4-nitrophthalic acid) have been synthesized by hydrothermal reaction of Ag(i) salts with N-/O-donor ligands. Single-crystal X-ray diffraction indicated that these coordination polymers constructed from mononuclear or polynuclear silver building blocks exhibit three typical structure features from 1-D to 3-D frameworks. These compounds favour a slow release of Ag(+) ions leading to excellent and long-term antimicrobial activities, which is distinguished by their different topological structures, towards both Gram-negative bacteria, Escherichia coli (E. coli) and Gram-positive bacteria, Staphylococcus aureus (S. aureus). In addition, these compounds show good thermal stability and light stability under UV-vis and visible light, which are important characteristics for their further application in antibacterial agents.

  14. Two unusual 12-connected metal–organic coordination polymers with fcu net

    SciTech Connect

    Guo, Sheng-Qi; Tian, Dan; Luo, Yu-Hui; Chen, Xin; Zhang, Hong

    2013-09-15

    Two new three-dimensional 12-connected metal–organic coordination polymers, [Zn{sub 2}(bptc)(H{sub 2}O)]·C{sub 2}H{sub 5}OH·H{sub 2}O (1) and [Cd{sub 4}(bptc){sub 2}(bbi)(H{sub 2}O)]·H{sub 2}O (2) (H4bptc=biphenyl-2,5,2′,5′-tetracarboxylic acid, bbi=1,1′-(1,4-butanediyl)bis(imidazole)), have been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction analyses. All compounds are also characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRD). Topological analysis indicates that both 1 and 2 are 12-connected frameworks with fcu topology, which are based on cuboid cage and rob-like (Cd3) subunit as 12-connected nodes, respectively. Furthermore, the luminescence properties of the two compounds were discussed in detail. - Graphical abstract: Two new compounds with unusual 12-connected fcu topology display intriguing structural feature, as well as luminescence property. Display Omitted - Highlights: • Two new 3D metal–organic coordination polymers based on biphenyl-2,5,2′,5′-tetracarboxylic acid ligand have been synthesized. • Two compounds exhibit rare 12-connected fcu topology. • Photoluminescent property at room temperature has been investigated.

  15. Visible and NIR photoluminescence properties of a series of novel lanthanide-organic coordination polymers based on hydroxyquinoline-carboxylate ligands.

    PubMed

    Gai, Yan-Li; Xiong, Ke-Cai; Chen, Lian; Bu, Yang; Li, Xing-Jun; Jiang, Fei-Long; Hong, Mao-Chun

    2012-12-17

    A series of novel two-dimensional (2D) lanthanide coordination polymers with 4-hydroxyquinoline-2-carboxylate (H(2)hqc) ligands, [Ln(Hhqc)(3)(H(2)O)](n)·3nH(2)O (Ln = Eu (1), Tb (2), Sm (3), Nd (4), and Gd (5)) and [Ln(Hhqc)(ox)(H(2)O)(2)](n) (Ln = Eu (6), Tb (7), Sm (8), Tm (9), Dy (10), Nd (11), Yb (12), and Gd (13); H(2)ox = oxalic acid), have been synthesized under hydrothermal conditions. Complexes 1-5 are isomorphous, which can be described as a two-dimensional (2D) hxl/Shubnikov network based on Ln(2)(CO(2))(4) paddle-wheel units, and the isomorphous complexes 6-13 feature a 2D decker layer architecture constructed by Ln-ox infinite chains cross-linked alternatively by bridging Hhqc(-) ligands. The room-temperature photoluminescence spectra of complexes Eu(III) (1 and 6), Tb(III) (2 and 7), and Sm(III) (3 and 8) exhibit strong characteristic emissions in the visible region, whereas Nd(III) (4 and 11) and Yb(III) (12) complexes display NIR luminescence upon irradiation at the ligand band. Moreover, the triplet state of H(2)hqc matches well with the emission level of Eu(III), Tb(III), and Sm(III) ions, which allows the preparation of new optical materials with enhanced luminescence properties.

  16. Localized cell stimulation by nitric oxide using a photoactive porous coordination polymer platform

    PubMed Central

    Diring, Stéphane; Wang, Dan Ohtan; Kim, Chiwon; Kondo, Mio; Chen, Yong; Kitagawa, Susumu; Kamei, Ken-ichiro; Furukawa, Shuhei

    2013-01-01

    Functional cellular substrates for localized cell stimulation by small molecules provide an opportunity to control and monitor cell signalling networks chemically in time and space. However, despite improvements in the controlled delivery of bioactive compounds, the precise localization of gaseous biomolecules at the single-cell level remains challenging. Here we target nitric oxide, a crucial signalling molecule with site-specific and concentration-dependent activities, and we report a synthetic strategy for developing spatiotemporally controllable nitric oxide-releasing platforms based on photoactive porous coordination polymers. By organizing molecules with poor reactivity into polymer structures, we observe increased photoreactivity and adjustable release using light irradiation. We embed photoactive polymer crystals in a biocompatible matrix and achieve precisely controlled nitric oxide delivery at the cellular level via localized two-photon laser activation. The biological relevance of the exogenous nitric oxide produced by this strategy is evidenced by an intracellular change in calcium concentration, mediated by nitric oxide-responsive plasma membrane channel proteins. PMID:24158008

  17. 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.

  18. Homochiral nickel coordination polymers based on salen(Ni) metalloligands: synthesis, structure, and catalytic alkene epoxidation.

    PubMed

    Huang, Yuanbiao; Liu, Tianfu; Lin, Jingxiang; Lü, Jian; Lin, Zujin; Cao, Rong

    2011-03-21

    One-dimensional (1D) homochiral nickel coordination polymers [Ni(3)(bpdc)(RR-L)(2)·(DMF)](n) (2R, RR-L = (R,R)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene), bpdc = 4,4'-biphenyldicarboxylic acid) and [Ni(3)(bpdc)(SS-L)(2)·(DMF)](n) (2S, SS-L = (S,S)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) based on enantiopure pyridyl-functionalized salen(Ni) metalloligand units NiL ((1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene))Ni(II)) have been synthesized and characterized by microanalysis, IR spectroscopy, solid-state UV-vis spectroscopy, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, cyclic voltammetric measurement, and powder and single crystal X-ray diffraction. Each NiL as unbridging pendant metalloligand uses one terminal pyridyl group to coordinate achiral unit (nickel and bpdc(2-)) building a helical chain, while the other pyridyl group remains uncoordinated. Both 2R and 2S contain left- and right-handed helical chains made of the achiral building blocks, while the NiL as remote external chiral source is perpendicular to the backbone of the helices. The nickel coordination polymers 2R and 2S containing unsaturated active nickel center in metalloligand NiL can be used as self-supported heterogeneous catalysts. They show catalytic activity comparable with their homogeneous counterpart in alkene epoxidation and exhibit great potential as recyclable catalysts.

  19. A series of phenyl sulfonate metal coordination polymers as catalysts for one-pot Biginelli reactions under solvent-free conditions.

    PubMed

    Wang, Jin-Hua; Tang, Gui-Mei; Wang, Yong-Tao; Cui, Yue-Zhi; Wang, Jun-Jie; Ng, Seik Weng

    2015-10-28

    Three new metal coordination polymers, namely, [Co(DPP)2(H2O)2]·(BS)2·2H2O (1), [Co(DPP)2(H2O)2]·(ABS)2·2H2O (2) and [Co(DPP)2(MBS)2] (3) [DPP = 1,3-di(pyridin-4-yl)propane, BS = phenyl sulfonic acid, ABS = p-aminobenzene sulfonic acid, MBS = p-methylbenzene sulfonic acid] were obtained under hydrothermal conditions. Complexes 1-3 were structurally characterized using X-ray single-crystal diffraction, XRD and IR spectroscopy. Both complexes 1 and 2 display a 1D tape structure. Meanwhile, complex 3 exhibits a 2D layer and further stacks via C-Hπ interactions to generate a three-dimensional supramolecular architecture. These three metal coordination polymers have been applied as catalysts for the green synthesis of a variety of 3,4-dihydropyrimidin-2(1H)-ones under solvent-free conditions through the Biginelli reaction. Interestingly, the catalysis products have been obtained in high yields under eco-friendly synthesis conditions.

  20. Synthesis of Coordination Polymers of Tetravalent Actinides (Uranium and Neptunium) with a Phthalate or Mellitate Ligand in an Aqueous Medium.

    PubMed

    Martin, Nicolas P; März, Juliane; Volkringer, Christophe; Henry, Natacha; Hennig, Christoph; Ikeda-Ohno, Atsushi; Loiseau, Thierry

    2017-03-06

    Four metal-organic coordination polymers bearing uranium or neptunium have been hydrothermally synthesized from a tetravalent actinide chloride (AnCl4) and phthalic (1,2-H2bdc) or mellitic (H6mel) acid in aqueous media at 130 °C. With the phthalate ligand, two analogous assemblies ([AnO(H2O)(1,2-bdc)]2·H2O; An = U(4+) (1) or Np(4+) (2)) have been isolated, in which the square-antiprismatic polyhedra of AnO8 are linked to each other via μ3-oxo groups with an edge-sharing mode to materialize infinite zigzag ribbons. The phthalate molecules play a role in connecting the adjacent zigzag chains to build a two-dimensional (2D) network. Water molecules are bonded to the actinide center or found intercalated between the layers. With the mellitate ligand, two distinct structures have been identified. The uranium-based compound [U2(OH)2(H2O)2(mel)] (3) exhibits a three-dimensional (3D) structure composed of the dinuclear units of UO8 polyhedra (square antiprism), which are further linked via the μ2-hydroxo groups. The mellitate linkers use their carboxylate groups to connect the dinuclear units, eventually building a 3D framework. The compound obtained for the neptunium mellitate ([(NpO2)10(H2O)14(Hmel)2]·12H2O (4)) reveals oxidation of the initial Np(IV) to Np(V) under the applied hydrothermal synthetic conditions, yielding the neptunyl(V) (NpO2(+)) unit with a pentagonal-bipyramidal NpO7 environment. This further leads to the formation of a layered assembly of the square-frame NpO7 sheets via the bridging oxygen atoms from the neptunyl oxo groups, which further coordinate to the pentagonal equatorial coordination plane of the adjacent neptunium unit (i.e., cation-cation interactions). In compound 4, the mellitate molecules act as bridging linkers between the NpO7 sheets by using four of their carboxylage groups, eventually building up a 3D structure.

  1. 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

  2. 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.

  3. In situ Oxidation of phenol and o-aminophenol in the channels of 3d-supramolecular coordination polymers

    NASA Astrophysics Data System (ADS)

    Etaiw, Safaa El-Din H.; Werida, Amal H.

    2010-09-01

    The host attractive properties of supramolecular coordination polymers of the type _infty^3 [(R3Sn)3FeIII(CN)6], where R = methyl (I), n-butyl (II), and phenyl (III), afford the ability to be used as effective oxidizing reagents for phenol and o-aminophenol forming new host-guest supramolecular coordination polymers. Phenol was oxidized to 1,4-benzoquinone while o-aminophenol was oxidized to poly-o-aminophenol by the polymers I and II and to 2-aminophenoxazin-3-one by the polymer III. The oxidation products were investigated by methods of spectroscopy and high-performance liquid chromatography. The redox reactions were characterized by first-order kinetics. Moreover, mechanisms of the oxidation processes of phenol and o-aminophenol have been proposed.

  4. 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%.

  5. Hand Ground Nanoscale Zn(II)-Coordination Polymers Derived from NSAIDs: Cell Migration Inhibition of Human Breast Cancer Cells.

    PubMed

    Dastidar, Parthasarathi; Paul, Mithun; Sarkar, Koushik; Deb, Jolly

    2017-02-25

    Increased level of intracellular prostaglandin E2 (PGE2) has been linked with the unregulated cancer cell migration that often leads to metastasis. Non-steroidal-anti-inflammatory-drugs (NSAIDs) are known inhibitors of cyclooxygenase (COX) enzymes responsible for increased PGE2 concentration in inflammated as well as cancer cells. In this article, we demonstrated that NSAID derived Zn(II)-coordination polymers were able to inhibit cell migration of human breast cancer cells. Various NSAIDs were anchored to a series of 1D Zn(II)-coordination polymers via carboxylate-Zn coordination and fully characterized by single crystal X-ray diffraction. Hand grinding in laboratory mortar and pastel resulted in nano-scale coordination polymers, for the first time, suitable for biological studies. Two such hand ground nano-scale coordination polymers namely NCP1a and NCP2a containing naproxen (a well-studied NSAID) were successfully internalized within the human breast cancer cells MDA-MD-231 as evident from cellular imaging using fluorescence microscope, were able to kill the cancer cells (MTT assay) more efficiently than the corresponding mother drug naproxen and most importantly inhibited significantly the cancer cell migration thereby displaying anti-cancer activity.

  6. 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.

  7. 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).

  8. 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.

  9. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    PubMed

    Rood, Jeffrey A; Huttenstine, Ashley L; Schmidt, Zachery A; White, Michael R; Oliver, Allen G

    2014-06-01

    Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF is N,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT-IR and (1)H NMR spectroscopy and elemental analyses.

  10. 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

  11. 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.

  12. Coordination Polymer Nanoglue: Robust Adhesion Based on Collective Lamellar Stacking of Nanoplates.

    PubMed

    Zhao, Yanyi; Li, Wenwu; Jiang, Xiangfen; Li, Fengqiong; Li, Xin; Zhang, Wei; Jiang, Ji-Sen; Liu, Jian; Ariga, Katsuhiko; Hu, Ming

    2017-03-15

    Despite a continuously growing interest in integration of coordination polymers (CPs) colloids towards functional materials, collective properties of the CPs colloids have rarely been addressed mainly due to the difficulty in assembling pure CPs colloids into superstructures with impressive mechanical strength. We demonstrated that CPs nanoplates could stack together spontaneously upon drying of the slurry of the nanoplates. The stacked CPs nanoplates could work like polymeric adhesives. Versatile articles could be glued when the CPs nanoplates were sandwiched between two substrates. In addition, the CPs nanoplates themselves could form well-defined bulk-structures without using any additional adhesives. The anisotropic shape together with the lamellar stacking way of the CPs nanoplates were found to be the key points in leading to the adhesion and cohesion effect. The reasonable adhesion strength of the CPs nanoglues can allow the exploration of further application of integrated CPs colloids in the future.

  13. Control of molecular rotor rotational frequencies in porous coordination polymers using a solid-solution approach.

    PubMed

    Inukai, Munehiro; Fukushima, Tomohiro; Hijikata, Yuh; Ogiwara, Naoki; Horike, Satoshi; Kitagawa, Susumu

    2015-09-30

    Rational design to control the dynamics of molecular rotors in crystalline solids is of interest because it offers advanced materials with precisely tuned functionality. Herein, we describe the control of the rotational frequency of rotors in flexible porous coordination polymers (PCPs) using a solid-solution approach. Solid-solutions of the flexible PCPs [{Zn(5-nitroisophthalate)x(5-methoxyisophthalate)1-x(deuterated 4,4'-bipyridyl)}(DMF·MeOH)]n allow continuous modulation of cell volume by changing the solid-solution ratio x. Variation of the isostructures provides continuous changes in the local environment around the molecular rotors (pyridyl rings of the 4,4'-bipyridyl group), leading to the control of the rotational frequency without the need to vary the temperature.

  14. 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.

  15. Chemistry of porous coordination polymers having multimodal nanospace and their multimodal functionality.

    PubMed

    Seo, Joobeom; Sakamoto, Hirotoshi; Matsuda, Ryotaro; Kitagawa, Susumu

    2010-01-01

    Remarkable advances in the recent development of porous coordination polymers (PCPs) or metal organic frameworks (MOFs) have paved the way toward functional chemistry having potential application such as molecular storage, separation, and catalysis. Moreover flexible PCPs, which are structurally transformable depending upon guest molecules adsorption/desorption, have received much attention because they provide unique properties, dissimilar to those of zeolites. PCPs can be categorized into structurally monomodal and multimodal classes. Monomodal PCPs possess single uniform pores in the framework. In contrast, multimodal PCPs have more than two types of pores in the framework. Interpenetrated PCPs can possess more than two types of pores with different sizes and shapes in the same framework depending on relative position of individual motifs, resulting in multimodal PCPs. Moreover, interpenetrated PCPs have several advantages, such as high thermal stability, flexibility, and ultramicropore for effective adsorption. In this review, chemistry of PCPs based on monomodal and multimodal PCPs are summarized and discussed.

  16. Substituent-induced effects on dimensionality in cadmium isophthalate coordination polymers containing 3-pyridylisonicotinamide

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    Hydrothermal treatment of cadmium nitrate, a 5-substituted isophthalic acid, and 3-pyridylisonicotinamide (3-pina) resulted in three coordination polymers whose dimensionality depended critically on the nature of the aromatic ring substituent. These three new phases were characterized by single crystal X-ray diffraction. {[Cd(hip)(3-pina)(H2O)2]·2H2O}n (1, hip = 5-hydroxyisophthalate) and {[Cd(meoip)(3-pina)(H2O)2]·H2O}n (2, meoip = 5-methoxyisophthalate) both manifest simple 1-D chain structures with pendant 3-pina ligands. [Cd(mip)(3-pina)]n (3, mip = 5-methylisophthalate) possesses [Cd(mip)]n 1-D chains featuring {Cd2(OCO)2} dimeric units, linked by tethering 3-pina ligands into a non-interpenetrated 3-D 6-connected 41263 pcu network. Luminescent behavior in all cases is attributed to intra-ligand molecular orbital transitions.

  17. Water stability of microporous coordination polymers and the adsorption of pharmaceuticals from water.

    PubMed

    Cychosz, Katie A; Matzger, Adam J

    2010-11-16

    The stability of a variety of microporous coordination polymers (MCPs) to water-containing solutions was studied using powder X-ray diffraction. It was determined that the stability of the MCP is related to the metal cluster present in the structure with trinuclear chromium clusters more stable than copper paddlewheel clusters which are more stable than basic zinc acetate clusters. Zn(2-methylimidizolate)(2) was found to be more water stable than zinc MCPs with carboxylate linkers; however, extended exposure to water led to decomposition of all zinc-based MCPs. Matériaux de l'Institut Lavoisier (MIL)-100 was also found to be completely water stable and was used to adsorb the pharmaceuticals furosemide and sulfasalazine from water with large uptakes achievable at low concentrations, indicating that the adsorption of wastewater contaminants may be a feasible application for these materials.

  18. Cyano-Bridged Trimetallic Coordination Polymer Nanoparticles and Their Thermal Decomposition into Nanoporous Spinel Ferromagnetic Oxides.

    PubMed

    Zakaria, Mohamed B; Hossain, Md Shahriar A; Shiddiky, Muhammad J A; Shahabuddin, Mohammed; Yanmaz, Ekrem; Kim, Jung Ho; Belik, Alexei A; Ide, Yusuke; Hu, Ming; Tominaka, Satoshi; Yamauchi, Yusuke

    2016-10-10

    The synthesis of a novel family of cyano-bridged trimetallic coordination polymers (CPs) with various compositions and shapes has been reported by changing the compositional ratios of Fe, Co, and Ni species in the reaction system. In order to efficiently control the nucleation rate and the crystal growth, trisodium citrate dihydrate plays an important role as a chelating agent. After the obtained cyano-bridged trimetallic CPs undergo thermal treatment in air at three different temperatures (250, 350, and 450 °C), nanoporous spinel metal oxides are successfully obtained. Interestingly, the obtained nanoporous metal oxides are composed of small crstalline grains, and the grains are oriented in the same direction, realizing pseudo-single crystals with nanopores. The resultant nanoporous spinel oxides feature interesting magnetic properties. Cyano-bridged multimetallic CPs with various sizes and shapes can provide a pathway toward functional nanoporous metal oxides that are not attainable from simple cyano-bridged CPs containing single metal ions.

  19. Modular design of domain assembly in porous coordination polymer crystals via reactivity-directed crystallization process.

    PubMed

    Fukushima, Tomohiro; Horike, Satoshi; Kobayashi, Hirokazu; Tsujimoto, Masahiko; Isoda, Seiji; Foo, Maw Lin; Kubota, Yoshiki; Takata, Masaki; Kitagawa, Susumu

    2012-08-15

    The mesoscale design of domain assembly is crucial for controlling the bulk properties of solids. Herein, we propose a modular design of domain assembly in porous coordination polymer crystals via exquisite control of the kinetics of the crystal formation process. Employing precursors of comparable chemical reactivity affords the preparation of homogeneous solid-solution type crystals. Employing precursors of distinct chemical reactivity affords the preparation of heterogeneous phase separated crystals. We have utilized this reactivity-directed crystallization process for the facile synthesis of mesoscale architecture which are either solid-solution or phase-separated type crystals. This approach can be also adapted to ternary phase-separated type crystals from one-pot reaction. Phase-separated type frameworks possess unique gas adsorption properties that are not observed in single-phasic compounds. The results shed light on the importance of crystal formation kinetics for control of mesoscale domains in order to create porous solids with unique cooperative functionality.

  20. A luminescent coordination polymer based on a π-conjugated ligand: Syntheses, structure and luminescent property

    NASA Astrophysics Data System (ADS)

    Li, Dan-Yang; Xie, Hua; Yao, Xiao-Qiang; Ma, Heng-Chang; Lei, Zi-Qiang; Liu, Jia-Cheng

    2017-04-01

    A new cadmium coordination polymer [Cd(DPFE)(adip)0.5(NO3)]n (1) has been synthesized hydrothermally from the self-assembly of the Cd2+ ion with a new π-conjugated rigid ligand DPFE and the adipic acid, where DPFE = 2,7-di(pyridin-4-yl)-9H-fluorene and H2adip = adipic acid. The structure of 1 was full characterized by elemental analysis, FT-IR spectroscopy and single crystal X-ray diffraction. Structural analysis reveals compound 1 is a dinuclear Cd(II) based two-dimensional (4,4) layer and two kinds of strong intramolecular π-π stacking interactions exist between pyridyl rings and benzene rings. In addition, the thermogravimetric analysis and solid-state luminescent properties have also been investigated.

  1. 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.

  2. Accelerating NLTE radiative transfer by means of the Forth-and-Back Implicit Lambda Iteration: A two-level atom line formation in 2D Cartesian coordinates

    NASA Astrophysics Data System (ADS)

    Milić, Ivan; Atanacković, Olga

    2014-10-01

    State-of-the-art methods in multidimensional NLTE radiative transfer are based on the use of local approximate lambda operator within either Jacobi or Gauss-Seidel iterative schemes. Here we propose another approach to the solution of 2D NLTE RT problems, Forth-and-Back Implicit Lambda Iteration (FBILI), developed earlier for 1D geometry. In order to present the method and examine its convergence properties we use the well-known instance of the two-level atom line formation with complete frequency redistribution. In the formal solution of the RT equation we employ short characteristics with two-point algorithm. Using an implicit representation of the source function in the computation of the specific intensities, we compute and store the coefficients of the linear relations J=a+bS between the mean intensity J and the corresponding source function S. The use of iteration factors in the ‘local’ coefficients of these implicit relations in two ‘inward’ sweeps of 2D grid, along with the update of the source function in other two ‘outward’ sweeps leads to four times faster solution than the Jacobi’s one. Moreover, the update made in all four consecutive sweeps of the grid leads to an acceleration by a factor of 6-7 compared to the Jacobi iterative scheme.

  3. Diverse manganese(II) coordination polymers derived from achiral/chiral imidazolium-carboxylate zwitterions and azide: structure and magnetic properties.

    PubMed

    Wang, Xuan; Li, Xiu-Bing; Yan, Ren-He; Wang, Yan-Qin; Gao, En-Qing

    2013-07-21

    Five Mn(II) coordination polymers containing azide and carboxylate as simultaneous bridges have been derived from different imidazolium-carboxylate zwitterionic ligands: 1-methyl-3-(carboxylatomethyl)imidazolium (L(1)), 1,3-bis(carboxylatomethyl)imidazolium (L(2)), (S,S)-, (R,R)-, and (R,S)-1,3-bis(1-carboxylatoethyl)imidazolium (S,S-L(3), R,R-L(3) and R,S-L(3)). The compounds are formulated as [Mn(L(1))(N3)2] (1), [Mn(L(2))(N3)] (2), [Mn(R,R-L(3))(N3)]·0.5CH3OH (3-R), [Mn(S,S-L(3))(N3)]·0.5CH3OH (3-S), [Mn(R,S-L(3))(N3)] (4). In compound 1, the neutral monocarboxylate zwitterion ligand (L(1)) leads to uniform chains with bis(azide)(carboxylate) bridges. For compounds 2-4, the anionic dicarboxylate zwitterions L(2) and L(3) lead to (azide)bis(carboxylate) bridges, but the overall coordination networks are different. In 2 and 3-S (or 3-R), chains with the (azide)bis(carboxylate) bridges are connected by L(2) and S,S-L(3) (or R,R-L(3)), respectively, to give achiral and chiral 2D coordination networks with different connecting topologies. In compounds 4, which is derived from the mesomeric ligand R,S-L(3), linear trinuclear units with the (azide)bis(carboxylate) bridges are linked by μ-1,3 azides to give 2D layers, and the layers are pillared into a 3D framework by the 1,3-dimethyleneimidazolium tethers. Magnetic analyses suggested that compounds 1-3 behave as 1D antiferromagnetic systems, while 4 shows canted antiferromagnetism with weak ferromagnetic ordering below T(C) = 12.4 K.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Trace Detection of Metalloporphyrin-Based Coordination Polymer Particles via Modified Surface-Enhanced Raman Scattering Assisted by Surface Metallization

    PubMed Central

    Caravella, Alessio

    2016-01-01

    This study proposed a facile method to detect metalloporphyrin-based coordination polymer particles (Z-CPPs) in aqueous solution by modified surface-enhanced Raman scattering (SERS). The SERS-active particles are photodeposited on the surface of Z-CPPs, offering an enhanced Raman signal for the trace detection of Z-CPPs. PMID:28115934

  10. 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

  11. 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.

  12. 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

  13. Three luminescent d{sup 10} metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu{sup 2+} ion and nitrobenzene

    SciTech Connect

    Wu, Wei-Ping; Liu, Ping; Liang, Yu-Tong; Cui, Lin; Xi, Zheng-Ping; Wang, Yao-Yu

    2015-08-15

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL{sub 2}]{sub n} (1) and ([ML{sub 2}]·(H{sub 2}O)){sub n} (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu{sup 2+} ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed. - Graphical abstract: Three luminescent d{sup 10} metal coordination polymers with helical-layer based on 4-((2-methyl-1H-imidazol-1-yl)methyl)benzoic acid have been obtained. Compound 1 shows high selective detecting for Cu{sup 2+} ion in aqueous and nitrobenzene. - Highlights: • Three coordination polymers with chiral helical-layer have been obtained. • 1 Can luminescent detect Cu{sup 2+} ion in aqueous media and nitrobenzene. • Racemic mixture or mesomer compounds can be obtained by controlling the reaction conditions.

  14. Diversity of coordination modes in the polymers based on 3,3',4,4'-biphenylcarboxylate ligand

    SciTech Connect

    Du Xiaodi; Xiao Hongping; Zhou Xinhui; Wu Tao; You Xiaozeng

    2010-06-15

    Four new compounds [Ni{sub 2}(4,4'-bpy)(3,4-bptc)(H{sub 2}O){sub 4}]{sub n} (1), [Ni(4,4'-bpy)(3,4-H{sub 2}bptc)(H{sub 2}O){sub 3}]{sub n} (2), [Mn{sub 2}(2,2'-bpy){sub 4}(3,4-H{sub 2}bptc){sub 2}] (3) and {l_brace}[Mn(1,10-phen){sub 2}(3,4-H{sub 2}bptc)].4H{sub 2}O{r_brace}{sub n} (4) (3,4-H{sub 4}bptc=3,3',4,4'-biphenyltetracarboxylic acid, 4,4'-bpy=4,4'-bipyridine, 2,2'-bpy=2,2'-bipyridine, 1, 10-phen=1, 10-phenanthroline), have been prepared and structurally characterized. In all compounds, the derivative ligands of 3,4-H{sub 4}bptc (3,4-bptc{sup 4-} and 3,4-H{sub 2}bptc{sup 2-}) exhibit different coordination modes and lead to the formation of various architectures. Compounds 1 and 2 display the three-dimensional (3D) framework: 1 shows a 3,4-connected topological network with (8{sup 3})(8{sup 5}.10) topology symbol based on the coordination bonds while in 2, the hydrogen-bonding interactions are observed to connect the 1D linear chain generating a final 3D framework. 3 exhibits the 2D layer constructed from the hydrogen-bonding interactions between the dinuclear manganese units. Complex 4 shows the double layers motif through connecting the 1D zigzag chains with hydrogen-bonded rings. The thermal stability of 1-4 and magnetic property of 1 were also reported. - Graphical abstract: Four coordination compounds exhibiting four coordination modes of the 3,3',4,4'-biphenylcarboxylate ligand, with three of new in this system, are obtained showing diversified architectures.

  15. Syntheses, crystal structures, and luminescence of two lanthanide coordination polymers based on 5-(3‧,4‧-bis(tetrazol-5″-yl)phenoxy)isophthalic acid and 1,10-phenanthroline

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoli; Li, Congcong; Ai, Fengfeng; Qu, Xu; Liu, Kang

    2017-04-01

    Two new lanthanide coordination polymers, [Ln(btpa)(phen)2(OH)]n·nH2O (Ln= Tb 1, Pr 2) (H2btpa=5-(3‧,4‧-bis(tetrazol-5″-yl)phenoxy)isophthalic acid, phen=1,10-phenanthroline), have been successfully synthesized and structurally characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, TGA and powder X-ray diffraction analyses. Coordination polymers 1-2 are isomorphism structures, showing a 1D chain bearing hooks structure. LnⅢ ion in 1-2 adopt nine-coordinated mode to construct a tricapped trigonal prism configuration. The adjacent chains form a 2D supramolecular network via π … π stacking interactions between the pyridine rings of phen ligands. Then the neighbouring 2D supramolecular networks recognizing each other form a 3D supramolecular structure through π … π interaction between benzene rings of (btpa)2- ligands. The luminescence experiments show that TbIII complex exhibits typical metal-centered emissions in the visible region in the solid state.

  16. [Synthesis and structure of silver(I) coordination polymers with bis(pyridyl) ligands linked by an aromatic sulfonamide].

    PubMed

    Katagiri, Kosuke

    2014-01-01

    Aromatic sulfonamides exist in a synclinal conformation with the twisted structure arising from rotation around the S-N bond in both the solid state and in solution. Simple bidentate ligands containing the sulfonamide moiety can be extended to form elongated ligands, and optically active components can be added to form a versatile building block for the construction of coordination polymers with many structures. Mixing the simple ligands 1 and 2 and the elongated ligands 3 and 4 with different Ag(I) salts yielded the corresponding complexes [Ag(1)OTf]n (1a), [Ag(2)]n•nOTf(2a), [Ag(3)OTf]n (3a), [Ag(3)]n•nBF₄ (3b), [Ag(4)CH₃CN]n•nBF₄•nCHCl₃ (4b), and [Ag(4)]n•nSbF₆•nCH₄O (4c). Straight chains and racemic helical polymers were observed in the crystal structure of complexes 1a and 2a, respectively. In the crystal structures of complexes 3a and 4b, infinite 1D straight chains containing a T-shaped coordination geometry about the Ag(I) centers were formed by the reaction of ligands 3 or 4 with Ag(I) salts in CH₃CN/CHCl₃. A continuous 1D coordination polymer containing a racemic mixture of left- and right-handed helices formed in the crystal structure of complex 3b. Furthermore, a layered coordination polymer consisting of a racemic mixture of left- and right-handed polymers was observed from the crystal structure of complex 4c. The construction of optically pure left- or right-handed 1D helical polymers via the introduction of chiral functional groups on the nitrogen atom of the sulfonamide ligand is currently under investigation in our laboratory.

  17. 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.

  18. Synthesis, crystal structure and luminescence properties of lanthanide coordination polymers with a new semirigid bridging thenylsalicylamide ligand

    NASA Astrophysics Data System (ADS)

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

    2013-09-01

    Two new lanthanide coordination polymers based on a semirigid bridging thenylsalicylamide ligand {[Ln2L3(NO3)6]·(C4H8O2)2}∞ were obtained and characterized by elemental analysis, X-ray diffraction, IR and TGA measurements. The two compounds are isostructure and possess one dimensional trapezoid ladder-like chain built up from the connection of isolated LnO3(NO3)3 polyhedra (distorted monocapped antisquare prism) through the ligand. The photoluminescence analysis suggest that there is an efficient ligand-to-Ln(III) energy transfer in Tb(III) complex and the ligand is an efficient "antenna" for Tb(III). From a more general perspective, the results demonstrated herein provide the possibility of controlling the formation of the desired lanthanide coordination structure to enrich the crystal engineering strategy and enlarge the arsenal for developing excellent luminescent lanthanide coordination polymers.

  19. Chiral one- and two-dimensional silver(I)-biotin coordination polymers.

    PubMed

    Altaf, Muhammad; Stoeckli-Evans, Helen

    2013-02-01

    Reaction of biotin {C(10)H(16)N(2)O(3)S, HL; systematic name: 5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoic acid} with silver acetate and a few drops of aqueous ammonia leads to the deprotonation of the carboxylic acid group and the formation of a neutral chiral two-dimensional polymer network, poly[[{μ(3)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}silver(I)] trihydrate], {[Ag(C(10)H(15)N(2)O(3)S)]·3H(2)O}(n) or {[Ag(L)]·3H(2)O}(n), (I). Here, the Ag(I) cations are pentacoordinate, coordinated by four biotin anions via two S atoms and a ureido O atom, and by two carboxylate O atoms of the same molecule. The reaction of biotin with silver salts of potentially coordinating anions, viz. nitrate and perchlorate, leads to the formation of the chiral one-dimensional coordination polymers catena-poly[[bis[nitratosilver(I)]-bis{μ(3)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}] monohydrate], {[Ag(2)(NO(3))(2)(C(10)H(16)N(2)O(3)S)(2)]·H(2)O}(n) or {[Ag(2)(NO(3))(2)(HL)(2)]·H(2)O}(n), (II), and catena-poly[bis[perchloratosilver(I)]-bis{μ(3)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}], [Ag(2)(ClO(4))(2)(C(10)H(16)N(2)O(3)S)(2)](n) or [Ag(2)(ClO(4))(2)(HL)(2)](n), (III), respectively. In (II), the Ag(I) cations are again pentacoordinated by three biotin molecules via two S atoms and a ureido O atom, and by two O atoms of a nitrate anion. In (I), (II) and (III), the Ag(I) cations are bridged by an S atom and are coordinated by the ureido O atom and the O atoms of the anions. The reaction of biotin with silver salts of noncoordinating anions, viz. hexafluoridophosphate (PF(6)(-)) and hexafluoridoantimonate (SbF(6)(-)), gave the chiral double-stranded helical structures catena-poly[[silver(I)-bis{μ(2)-5-[(3aS,4S,6aR)-2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl]pentanoato}] hexafluoridophosphate], {[Ag(C(10)H(16)N(2)O(3)S)(2)](PF(6))}(n) or {[Ag(HL)(2)](PF(6

  20. Increased dimensionalities of zinc-diphenic acid coordination polymers by simultaneous or subsequent addition of neutral bridging ligands.

    PubMed

    Dietzel, Pascal D C; Blom, Richard; Fjellvåg, Helmer

    2006-01-28

    Three coordination polymers containing zinc and diphenic acid (H2dpa) were synthesised by solvothermal reaction. Zn(dpa)(H2O) is a one-dimensional coordination polymer that consists of parallel ladder-like chains. One carboxylate group of the diphenic acid coordinates two zinc atoms forming a dinuclear unit which composes the steps of the ladder. The other carboxylate connects to a zinc atom in the next step of the ladder. The fourth coordination site at the zinc atom is occupied by water. Attempts to crosslink the chains by replacing the water molecule with the neutral ligands triethylenediamine (dabco) or 4,4'-bipyridyl lead to the compounds Zn2(dpa)2(dabco) and Zn(dpa)(4,4'-bpy). Their structures can be rationalised as being derived from action of the neutral ligand on Zn(dpa)(H2O), and while they are most conveniently prepared in a one-pot synthesis, it is also possible to obtain them by exposing Zn(dpa)(H2O) to the respective neutral ligand. Zn2(dpa)2(dabco) is a layered two-dimensional coordination polymer in which dinculear zinc carboxylate paddle wheel units and the dabco ligand form infinite linear chains. The chains are interconnected by the dpa unit. The structure of Zn(dpa)(4,4'-bpy) consists of two identical interpenetrating three-dimensional networks. In the network, helical Zn(dpa) chains are interconnected by the rigid 4,4'-bipyridine ligand. Thermogravimetric analysis indicates a high thermal stability of this coordination polymer with decomposition occurring in the range 350-450 degrees C. This is complemented by X-ray thermodiffractometry that indicates a phase transition at 337 degrees C and the final loss of crystallinity at 427 degrees C. The room temperature phase expands drastically along one axis and contracts along the other two axes on heating.

  1. Structural variability, Hirshfeld surface analysis and properties of three Zn(II) coordination polymers based on flexible bis(thiabendazole) and aromatic dicarboxylate co-ligands

    NASA Astrophysics Data System (ADS)

    Chang, Hai-Ning; Liu, Ce; Hao, Zeng-Chuan; Cui, Guang-Hua

    2017-02-01

    Three zinc(II) coordination polymers (CPs), {[Zn(L)0.5(tbta)]·0.5 L·2.5H2O}n (1), {[Zn(L)0.5(mip)]·H2O}n (2) and {[Zn(L)0.5(npht)(H2O)]·0.5H2O}n (3) (L = 1,4-bis(thiabendazole)butane, H2tbta = tetrabromoterephthalic acid, H2mip = 5-methylisophthalic acid, H2npht = 3-nitrophthalic acid) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that CP 1 shows a 2D honeycomb-like (6, 3) network. CP 2 displays a hybrid helical chain, and further assembled into a 2D supramolecular layer via weak Csbnd H⋯O hydrogen bonding interactions, whereas CP 3 is a right-handed helical chain and finally extended into a 3D supramolecular structure by classical Osbnd H⋯O hydrogen bonds and π-π stacking interactions. Further, the Hirshfeld surfaces, fingerprint plots, fluorescence properties and catalytic performances of three CPs for the degradation of methyl orange dye in a Fenton-like process have been investigated.

  2. Copper(II) Coordination Polymers Self-Assembled from Aminoalcohols and Pyromellitic Acid: Highly Active Precatalysts for the Mild Water-Promoted Oxidation of Alkanes.

    PubMed

    Fernandes, Tiago A; Santos, Carla I M; André, Vânia; Kłak, Julia; Kirillova, Marina V; Kirillov, Alexander M

    2016-01-04

    Three novel water-soluble 2D copper(II) coordination polymers-[{Cu2(μ2-dmea)2(H2O)}2(μ4-pma)]n·4nH2O (1), [{Cu2(μ2-Hedea)2}2(μ4-pma)]n·4nH2O (2), and [{Cu(bea)(Hbea)}4(μ4-pma)]n·2nH2O (3)-were generated by an aqueous medium self-assembly method from copper(II) nitrate, pyromellitic acid (H4pma), and different aminoalcohols [N,N-dimethylethanolamine (Hdmea), N-ethyldiethanolamine (H2edea), and N-benzylethanolamine (Hbea)]. Compounds 2 and 3 represent the first coordination polymers derived from H2edea and Hbea. All the products were characterized by infrared (IR), electron paramagnetic resonance (EPR), and ultraviolet-visible light (UV-vis) spectroscopy, electrospray ionization-mass spectroscopy (ESI-MS(±)), thermogravimetric and elemental analysis, and single-crystal X-ray diffraction (XRD), which revealed that their two-dimensional (2D) metal-organic networks are composed of distinct dicopper(II) or monocopper(II) aminoalcoholate units and μ4-pyromellitate spacers. From the topological viewpoint, the underlying 2D nets of 1-3 can be classified as uninodal 4-connected layers with the sql topology. The structures of 1 and 2 are further extended by multiple intermolecular hydrogen bonds, resulting in three-dimensional (3D) hydrogen-bonded networks with rare or unique topologies. The obtained compounds also act as highly efficient precatalysts for the mild homogeneous oxidation, by aqueous H2O2 in acidic MeCN/H2O medium, of various cycloalkanes to the corresponding alcohols and ketones. Overall product yields up to 45% (based on cycloalkane) were attained and the effects of various reaction parameters were investigated, including the type of precatalyst and acid promoter, influence of water, and substrate scope. Although water usually strongly inhibits the alkane oxidations, a very pronounced promoting behavior of H2O was detected when using the precatalyst 1, resulting in a 15-fold growth of an initial reaction rate in the cyclohexane oxidation on

  3. Synthesis, crystal structures, and luminescent properties of Cd(II) coordination polymers assembled from semi-rigid multi-dentate N-containing ligand

    SciTech Connect

    Yuan, Gang; Shao, Kui-Zhan; Chen, Lei; Liu, Xin-Xin; Su, Zhong-Min; Ma, Jian-Fang

    2012-12-15

    Three new polymers, [Cd(L){sub 2}(H{sub 2}O){sub 2}]{sub n} (1), [Cd{sub 3}(L){sub 2}({mu}{sub 3}-OH){sub 2}({mu}{sub 2}-Cl){sub 2}(H{sub 2}O){sub 2}]{sub n} (2), {l_brace}[Cd{sub 2}(L){sub 2}(nic){sub 2}(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O{r_brace}{sub n} (3) (HL=5-(4-((1H-1,2,4-triazol-1-yl)methyl)phenyl)-1H-tetrazole, Hnic=nicotinic acid) have been prepared and structurally characterized. Compounds 1 and 2 display 2D monomolecular layers built by the inter-linking single helical chains and L{sup -} ligands connecting chain-like [Cd({mu}{sub 3}-OH)({mu}{sub 2}-Cl)]{sub n} secondary building units, respectively. Compound 3 is constructed from the mixed ligands and possesses a (3,4)-connected framework with (4{center_dot}8{sup 2})(4{center_dot}8{sup 2}{center_dot}10{sup 3}) topology. Moreover, the fluorescent properties of HL ligand and compounds 1-3 are also been investigated. - Graphical abstract: Three new coordination polymers based on the semi-rigid multidentate N-donor ligand have been successfully synthesized by hydrothermal reaction. Complexes 1 and 2 exhibit the 2D layers formed by inter-linking single helices and L{sup -} anions bridging 1D chain-like SBUs, respectively. Complex 3 is buit by L{sup -} and assistant nic{sup -} ligands connecting metal centers and possesses a (3,4)-connected framework with (4 Multiplication-Sign 8{sup 2})(4 Multiplication-Sign 8{sup 2} Multiplication-Sign 10{sup 3}) topology. Moreover, these complexes display fluorescent properties indicating that they may have potential applications as optical materials. Highlights: Black-Right-Pointing-Pointer Three Cd-compounds were prepared from semi-rigid HL ligand with different N-containing groups. Black-Right-Pointing-Pointer They exhibit diverse structures from 2D monomolecular layer to 3D covalent framework. Black-Right-Pointing-Pointer The HL ligands displayed various coordination modes under different reaction conditions. Black-Right-Pointing-Pointer These compounds exhibit

  4. Carboxylate ligands induced structural diversity of zinc(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties

    SciTech Connect

    Cheng, Hong-Jian Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin

    2015-12-15

    Solvothermal reactions of Zn(NO{sub 3}){sub 2}·6H{sub 2}O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H{sub 2}bdc), p-phenylenediacetic acid (p-H{sub 2}pda), benzophenone-4,4-dicarboxylic acid (H{sub 2}bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]{sub n} (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H_2O}{sub n} (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H_2O}{sub n} (3). Complexes 1–3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1–3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored. - Graphical abstract: Reactions of Zn(NO{sub 3}){sub 2} and 3,6-(1-imidazolyl)carbazole with 1,4-benzenedicarboxylic acid, p-phenylenediacetic acid or benzophenone-4,4-dicarboxylic acid afforded three coordination polymers with different topologies and photocatalytic activity. - Highlights: • Reactions of 1,4-H{sub 2}bdc, p-H{sub 2}pda or H{sub 2}bpda with 3,6-bmcz and Zn(II) gave three CPs. • Complex 1 is a 3D entanglement. • Complex 2 or 3 is a 3D supramolecular structure based on different 2D layers. • Complex 2 exhibited good catalytic activity of methylene blue photodegradation.

  5. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    NASA Astrophysics Data System (ADS)

    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)2]·1.5H2O}n (1), [Cd(5-Brnic)2]n (2), [Co(5-Brnic)2(H2O)2]n (3), [Zn(5-Brnic)2(H2biim)]n (4), {[Cd(5-Brnic)2(phen)]·H2O}n (5), and [Pb(5-Brnic)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 (H2biim) 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.

  6. Modulation of the Structure and Properties of Uranyl Ion Coordination Polymers Derived from 1,3,5-Benzenetriacetate by Incorporation of Ag(I) or Pb(II).

    PubMed

    Thuéry, Pierre; Harrowfield, Jack

    2016-07-05

    Reaction of uranyl nitrate with 1,3,5-benzenetriacetic acid (H3BTA) in the presence of additional species, either organic bases or their conjugate acids or metal cations, has provided 12 new crystalline complexes, all but one obtained under solvo-hydrothermal conditions. The complexes [C(NH2)3][UO2(BTA)]·H2O (1) and [H2NMe2][UO2(BTA)] (2) crystallize as one- or two-dimensional (1D or 2D) assemblies, respectively, both with uranyl tris-chelation by carboxylate groups and hydrogen-bonded counterions but different ligand conformations. One of the bound carboxylate units is replaced by chelating 1,10-phenanthroline (phen) or 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4phen) in the complexes [(UO2)3(BTA)2(phen)3]·4H2O (3) and [(UO2)3(BTA)2(Me4phen)3]·NMP·3H2O (4) (NMP = N-methyl-2-pyrrolidone), which are a 2D network with honeycomb topology and a 1D polymer, respectively. With silver(I) cations, [UO2Ag(BTA)] (5), a three-dimensional (3D) framework in which the ligand assumes various chelating/bridging coordination modes, and the aromatic ring is involved in Ag(I) bonding, is obtained. A series of seven heterometallic complexes results when lead(II) cations and N-chelating molecules are both present. The complexes [UO2Pb(BTA)(NO3)(bipy)] (6) and [UO2Pb2(BTA)2(bipy)2]·3H2O (7), where bipy is 2,2'-bipyridine, crystallize from the one solution, as 1D and 2D assemblies, respectively. The two 1D coordination polymers [UO2Pb(BTA)(HCOO)(phen)] (8 and 9), again obtained from the one synthesis, provide an example of coordination isomerism, with the formate anion bound either to lead(II) or to uranyl cations. Another 2D architecture is found in [(UO2)2Pb2(BTA)2(HBTA)(H2O)2(phen)2]·2H2O (10), which provides a possible example of a Pb-oxo(uranyl) "cation-cation" interaction. While [UO2Pb(BTA)(HCOO)0.5(NO3)0.5(Me2phen)] (11), where Me2phen is 5,6-dimethyl-1,10-phenanthroline, is a 1D assembly close to those in 6 and 8, [UO2Pb2(BTA)2(Me4phen)2] (12), obtained together with

  7. 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

  8. Reversible adsorption of a planar cyclic (H2O)6 cluster held in a 2D CuII-coordination framework

    NASA Astrophysics Data System (ADS)

    Zhao, Yang; Lu, Hui; Yang, Le; Luo, Geng-Geng

    2015-05-01

    Coordination polymeric solid, {[Cu(btec)0.5(bpe)(H2O)2]ṡ(H2O)4}n (1) (H4btec = 1,2,4,5-benzenetetracarboxylic acid, and bpe = 1,2-bis(4-pyridyl)ethane), has been obtained by the solution phase ultrasonic synthesis techniques. The structure established through X-ray structural analysis shows that a centrosymmetric water hexamer with planar conformation structurally similar to aromatic benzene is unambiguously crystallized within the hydrophilic channel of 1. Water escapes at 150 °C but is re-absorbed using water vapor. The reversible formation of this water cluster was supported from powder X-ray diffraction (PXRD), FTIR spectra and TGA/DTA. The reversible dehydration/rehydration behaviors enable analysis of the nature of the intermolecular interactions that occur between the planar hexameric water and the resulting host framework. When the auxiliary ligand bpe was removed from the synthetic conditions, another complex {[Cu(btec)0.5(H2O)3]ṡH2O}n (2) only encapsulating a water dimer was afforded, which suggests bpe plays an important role in the formation of the framework and water clusters.

  9. Diffusion-coupled molecular assembly: structuring of coordination polymers across multiple length scales.

    PubMed

    Hirai, Kenji; Reboul, Julien; Morone, Nobuhiro; Heuser, John E; Furukawa, Shuhei; Kitagawa, Susumu

    2014-10-22

    Porous coordination polymers (PCPs) are an intriguing class of molecular-based materials because of the designability of framework scaffolds, pore sizes and pore surface functionalities. Besides the structural designability at the molecular scale, the structuring of PCPs into mesoscopic/macroscopic morphologies has attracted much attention due to the significance for the practical applications. The structuring of PCPs at the mesoscopic/macroscopic scale has been so far demonstrated by the spatial localization of coordination reactions on the surface of templates or at the phase boundaries. However, these methodologies have never been applied to the fabrication of solid-solution or multivariate metal-organic frameworks (MOFs), in which multiple components are homogeneously mixed. Herein, we demonstrate the structuring of a box-type superstructure comprising of a solid-solution PCP by integrating a bidirectional diffusion of multiple organic ligands into molecular assembly. The parent crystals of [Zn2(ndc)2(bpy)]n were placed in the DMF solution of additional organic component of H2bdc, and the temperature was rapidly elevated up to 80 °C (ndc = 1,4-naphthalenedicarboxylate, bpy = 4,4'-bipyridyl, bdc = 1,4-benzenedicarboxylate). The dissolution of the parent crystals induced the outward diffusion of components; contrariwise, the accumulation of the other organic ligand of H2bdc induced the inward diffusion toward the surface of the parent crystals. This bidirectional diffusion of multiple components spatially localized the recrystallization at the surface of cuboid parent crystals; therefore, the nanocrystals of a solid-solution PCP ([Zn2(bdc)1.5(ndc)0.5(bpy)]n) were organized into a mesoscopic box superstructure. Furthermore, we demonstrated that the box superstructures enhanced the mass transfer kinetics for the separation of hydrocarbons.

  10. Redox and catalysis 'all-in-one' infinite coordination polymer for electrochemical immunosensor of tumor markers.

    PubMed

    Zhang, Bing; Liu, Bingqian; Chen, Guonan; Tang, Dianping

    2015-02-15

    Prostate-specific antigen (PSA), as a glycoprotein enzyme encoded in humans by the KLK3 gene, is one of the most important biomarkers for the diagnosis and prognosis of prostate cancer. Herein, a new electrochemical immunosensor for sensitive determination of PSA was designed by using redox and catalysis 'all-in-one' infinite coordination polymer (PtNP@ICP) as signal tag on the polyamidoamine dendrimers modified electrode interface. To construct such 'all-in-one' PtNP@ICP nanostructures, the coordination polymerization was fully carried between metal ions and polydentate bridging ligands, and the PtNP was encapsulated into the ICP in the process of polymerization. The prepared PtNP@ICP nanocatalyst was characterized by transmission electron microscope (TEM), energy dispersive X-ray spectrometry (EDX), ultraviolet and visible (UV-vis) spectrophotometry and Fourier transform infrared spectroscope (FTIR). And the synthesized PtNP@ICP was utilized as signal tag for the label of PSA. With a sandwich-type immunoassay format, the conjugated signal tag on the transducer increased with the increasing PSA concentration in the sample thus enhancing the signal of the electrochemical immunosensor due to the catalytic reduction toward H2O2 of the enveloped PtNP. Under optimal conditions, the current was proportional to the logarithm of PSA concentration ranging from 0.001 to 60 ng/mL. The detection limit (LOD) was 0.3 pg/mL at 3 sB. The immunosensor displayed an acceptable reproducibility, stability and selectivity. In addition, the methodology was evaluated with human serum specimens receiving good correlation with results from commercialized enzyme-linked immunosorbent assay (ELISA) method.

  11. Solvothermal self-assembly of Cd(2+) coordination polymers with supramolecular networks involving N-donor ligands and aromatic dicarboxylates: synthesis, crystal structure and photoluminescence studies.

    PubMed

    Rachuri, Yadagiri; Parmar, Bhavesh; Bisht, Kamal Kumar; Suresh, Eringathodi

    2017-03-14

    Two cadmium(ii) coordination polymers (CPs) of compositions {[Cd(H2O)4(4-BPDB)][BPDC]}n (CP1) and {[Cd(H2O)(BrIP)(BTTMB)]·4MeOH}n (CP2) have been synthesized by solvothermal methods and characterized by several analytical methods including SXRD (Single Crystal X-ray Diffraction). The structure of CP1 can be described as a 1D cationic chain, {[Cd(H2O)4(4-BPDB)](2+)}n and discrete BPDC counter anions. The structure of CP2 revealed an undulated 2D sql net comprising Cd(2+) nodes bridged by the ditopic N-donor, BTTMB and dicarboxylate BrIP involved in μ2-η(1)η(1)η(1)η(1) coordination. Supramolecular interactions in both CPs generate 3D hydrogen bonded architectures. The solid state fluorescence properties of these d(10) metal ion containing CPs have been investigated. Fluorescence emission of CP1 suspended in acetonitrile is observed to be selectively quenched by acetone (LOD = 0.15 mM) over other common laboratory solvents.

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

    SciTech Connect

    Zhuang Guilin; Chen Wulin; Zheng Jun; Yu Huiyou; Wang Jianguo

    2012-08-15

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H{sub 3}SIDA) and Ln(NO{sub 3}){sub 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 Gd{sup 3+} ions for anti-anti and syn-anti carboxylate bridges are -1.0 Multiplication-Sign 10{sup -3} and -5.0 Multiplication-Sign 10{sup -3} cm{sup -1}, respectively, which reveals weak antiferromagnetic interaction in 4. - Graphical abstract: Four lanthanide coordination polymers with N-(sulfoethyl) iminodiacetic acid were obtained under hydrothermal condition and reveal the weak antiferromagnetic coupling between two Gd{sup 3+} ions by Quantum Monte Carlo studies. Highlights: Black-Right-Pointing-Pointer Four lanthanide coordination polymers of H{sub 3}SIDA ligand were obtained. Black-Right-Pointing-Pointer Lanthanide ions play an important role in their structural diversity. Black-Right-Pointing-Pointer Magnetic measure exhibits that compound 4 features antiferromagnetic property. Black-Right-Pointing-Pointer Quantum Monte Carlo studies reveal the coupling parameters of two Gd{sup 3+} ions.

  13. Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene ligand

    NASA Astrophysics Data System (ADS)

    Shao, Min; Li, Ming-Xing; Lu, Li-Ruo; Zhang, Heng-Hua

    2016-09-01

    Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu3(CN)3(tib)]n (1), [Cu4(CN)4(tib)]n (2), and [Cu2(CN)2(tib)]n (3), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ2-cyanides and a μ3-cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250-350 °C. Complexes 1-3 show similar orange emission band at 602 nm originating from LMCT mechanism.

  14. A New Structural Family of Gas-Sorbing Coordination Polymers Derived from Phenolic Carboxylic Acids.

    PubMed

    White, Keith F; Abrahams, Brendan F; Babarao, Ravichandar; Dharma, A David; Hudson, Timothy A; Maynard-Casely, Helen E; Robson, Richard

    2015-12-07

    The structure of Li(inox)⋅2/3 DMF (inox(-) =the N-oxide of the isonicotinate anion) consists of a 3D framework with solvent-filled, square cross-section channels of approximate dimensions 5.5×5.5 Å. Unfortunately, the Li(inox) framework is unstable upon removal of DMF from the channels. When the structurally related 4-hydroxybenzoic acid (H2 hba) was used in place of Hinox, and Zn(2+) in place of the Li(+) , a structurally similar but more robust network, Zn(hba), was obtained; the isostructural compound, Co(hba), may also be prepared. Longer ligands with phenolate and carboxylate functional groups at opposite ends, such as the dianions of 4-coumaric acid (H2 cma) and 4'-hydroxy-4-biphenylcarboxylic acid (H2 hbpc), in combination with Zn(2+) yield Zn(cma) and Zn(hbpc) frameworks, respectively, with the same PtS topology but with larger channels. The coordination polymers remain intact after desolvation and exhibit microporosity, showing the ability to sorb significant quantities of CO2 , CH4 , and H2 .

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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

    2015-07-07

    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.

  20. Coordination chemistry of mercury(ii) with 2-pyridylnitrones: monomers to polymers.

    PubMed

    Azizpoor Fard, Mahmood; Behnia, Ava; Puddephatt, Richard J

    2017-03-14

    The coordination chemistry of mercury(ii) halides, HgX2, X = Cl, Br, I, with N-methyl-α-(2-pyridyl)nitrone, L1, and N-t-butyl-α-(2-pyridyl)nitrone, L2, is reported. The structures of 1 : 1 complexes [HgX2L], X = Cl, L = L1; X = Br, L = L2, 2 : 1 complexes [(HgX2)2L], X = Br or I, L = L1; X = Cl or I, L = L2, and a unique compound [(HgBr2)5(L2)3] have been determined. In the 1 : 1 and 1 : 2 complexes, the ligand L1 adopts the anti conformation, and is either monodentate or bridging, while the ligand L2 adopts the syn conformation and acts as a chelate ligand. In the compound [(HgBr2)5(L2)3] the ligand L2 is present in both syn-chelate and anti-bridging bonding modes. Secondary intermolecular bonding, involving OHg or XHg interactions, can lead to association of the molecular compounds to form polymers of several kinds. In solution, the complexes are labile and the crystalline products do not necessarily reflect the reaction stoichiometry.

  1. 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.

  2. Natural gas purification using a porous coordination polymer with water and chemical stability.

    PubMed

    Duan, Jingui; Jin, Wanqin; Krishna, Rajamani

    2015-05-04

    Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we demonstrate a new PCP, [(Cu4Cl)(BTBA)8·(CH3)2NH2)·(H2O)12]·xGuest (PCP-33⊃guest), which shows high potential for purification of natural gas, separation of C2H2/CO2 mixtures, and selective removal of C2H2 from C2H2/C2H4 mixtures at ambient temperature. The lower binding energy of the framework toward these light hydrocarbons indicates the reduced net costs for material regeneration, and meanwhile, the good water and chemical stability of it, in particular at pH = 2 and 60 °C, shows high potential usage under some harsh conditions. In addition, the adsorption process and effective site for separation was unravelled by in situ infrared spectroscopy studies.

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

    PubMed Central

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

    2014-01-01

    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 tumor xenograft models evaluated, including CT26 colon cancer, H460 lung cancer, and AsPC-1 pancreatic cancer, pegylated NCPs show superior potency and efficacy compared to free drugs. As the first example of using NCPs as nanotherapeutics with enhanced antitumor activities, this study establishes NCPs as a promising drug delivery platform for cancer therapy. PMID:24964370

  4. Heteronuclear, mixed-metal Ag(I)-Mn(II) coordination polymers with bridging N-pyridinylisonicotinohydrazide ligands: synthesis, crystal structures, magnetic and photoluminescence properties.

    PubMed

    Bikas, Rahman; Hosseini-Monfared, Hassan; Vasylyeva, Vera; Sanchiz, Joaquín; Alonso, Javier; Barandiaran, Jose Manuel; Janiak, Christoph

    2014-08-21

    Mixed-metal dicyanoargentate-bridged coordination polymers of Ag(i)-Mn(ii) have been prepared and their structure and magnetic properties were determined. Reaction of manganese(ii) chloride and potassium dicyanoargentate(i) with (X)(pyridin-2-ylmethylene)isonicotinohydrazide ligands (HL(1) X = Ph, HL(2) X = Me, HL(3) X = H) produced the coordination polymer 2D-[Mn(μ-L(1))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n (), 1D-{[Mn(L(2))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]CH3OH}n () and [Mn(L(3))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n () in good yields. Trinuclear {Mn(μ-L(1))Mn(μ-L(1))Mn} and [Ag(CN)2](-) building units form a two-dimensional slab in and 1D strands in . Variable temperature magnetic susceptibility measurements showed that despite the long distance among the high spin Mn(ii) ions [10.4676(12) Å and 10.522(1) Å, for and , respectively], weak antiferromagnetic coupling takes place through the long NC-Ag-CN bridge. The best fit parameters to the model led to the magnetic coupling constant of J = -0.1 and J = -0.47 cm(-1) for and , respectively. The photoluminescence behaviour of compounds and was studied. The spectrum of compound shows a broad emission centered at about 450 nm and two excitation maxima at 270 and 310 nm.

  5. 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.

  6. Self-assembled copper(II) coordination polymers derived from aminopolyalcohols and benzenepolycarboxylates: structural and magnetic properties.

    PubMed

    Kirillov, Alexander M; Karabach, Yauhen Y; Haukka, Matti; Guedes da Silva, M Fatima C; Sanchiz, Joaquin; Kopylovich, Maximilian N; Pombeiro, Armando J L

    2008-01-07

    The new copper(II) or copper(II)/sodium(I) 1D coordination polymers [Cu2(Hmdea)2(mu-H2O)(mu2-tpa)]n.2nH2O (1), [Cu2(H2tipa)2(mu2-ipa)]n.4nH2O (2), [Cu2(H2tea)2Na(H2O)2(mu2-tma)]n.6nH2O (3), [Cu2(H2tea)2(mu2-ipa)]n.nH2O (4a), and [Cu2(H2tea)2{mu3-Na(H2O)3}(mu3-ipa)]n(NO3)n.0.5nH2O (4b) have been prepared in aqueous medium by self-assembly from copper(II) nitrate, aminopolyalcohols [methyldiethanolamine (H2mdea), triisopropanolamine (H3tipa), and triethanolamine (H3tea)] as main chelating ligands and benzenepolycarboxylic acids [terephthalic (H2tpa), isophthalic (H2ipa), and trimesic (H3tma) acid] as spacers. They have been characterized by IR spectroscopy, elemental and single-crystal X-ray diffraction analyses, the latter indicating the formation of unusual multinuclear metal cores interconnected by various benzenepolycarboxylate spacers, leading to distinct wavelike, zigzag, or linear 1D polymeric metal-organic chains. These are further extended to 2D or 3D hydrogen-bonded supramolecular networks via extensive interactions with the intercalated crystallization water molecules. The latter are associated, also with aqua ligands, by hydrogen bonds resulting in acyclic (H2O)3 clusters in 1, (H2O)8 clusters in 2, infinite 1D water chains in 3, and disordered water-nitrate associates in 4b, all playing a key role in the structure stabilization and its extension to further dimensions. Variable-temperature magnetic susceptibility measurements have shown that 1-4 exhibit a moderately strong ferromagnetic coupling through the alkoxo bridge. The small Cu-O-Cu bridging angle and the large out-of-plane displacement of the carbon atom of the alkoxo group accounts for this behavior. The magnetic data have been analyzed by means of a dinuclear and a 1D chain model, and the magnetic parameters have been determined. The magnetic exchange coupling in 3, to our knowledge, is the highest found in alkoxo-bridged copper(II) complexes.

  7. Highly effective heterogeneous chemosensors of luminescent silica@coordination polymer core-shell micro-structures for metal ion sensing

    PubMed Central

    Cho, Won; Lee, Hee Jung; Choi, Sora; Kim, Yoona; Oh, Moonhyun

    2014-01-01

    Heterogeneous solid sensors are regarded as promising next-generation sensor due to their excellent chemical stability, low contamination, and excellent recyclability, despite their low sensitivity and weak signal. The dispersity and signals specifically from the exterior of solid sensors are critical aspects which define the sensing sensitivity and selectivity. A novel strategy for the preparation of ideal heterogeneous sensors based upon luminescent lanthanide coordination polymers (LnCP) has been demonstrated. Ideal heterogeneous sensors are systematically achieved by producing the sensors in small, uniform, and thin core-shell particles (silica@LnCP, Ln = Eu, Tb). Eventually, we found that the extremely small amount of well-structured silica@LnCP microsphere, less than ca. 1/400 compared to the amount of several known coordination polymer-based sensors, was sufficient to achieve a reliable Cu2+ sensing with even much greater sensitivity (ca. 550% improvement). PMID:25269855

  8. 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

    2016-11-05

    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.

  9. Three coordination polymers constructed from 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid: Synthesis, crystal structure and properties

    NASA Astrophysics Data System (ADS)

    Zhai, Dandan; Sun, Wujuan; Fan, Fei; Liao, Xuzhao; Chen, Sanping; Yang, Xuwu

    2017-04-01

    Three new coordination polymers, namely, {[Co2(TPA)(μ3-O)3]·0.5DMA}n (1), {[Co(H2TPA)(bibp)(H2O)3]·H2O}n (2) and {[Cd3(TPA)2(phen)4]·4H2O}n (3), (H3TPA = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid, bibp = 4,4'-bis(imidazolyl)biphenyl, phen = 1,10-phenanthroline and DMA = N,N-dimethylacetamide), have been synthesized under solvothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analysis. Polymer 1 exhibits a three-dimensional (3D) structure constructed from 5-connected secondary building units (SBUs) [Co3(μ3-O)] and 3-connected H3TPA ligands. Polymer 2 has a 1D zigzag polymer chain connected by H3TPA and bibp ligands. Polymer 3 features an unusual 3D framework with a (3,4,2)-connected {4; 6;8}{4; 62;83} topology. Moreover, the thermal stabilities of 1-3 and photoluminescence properties of 3 have been investigated. Magnetic susceptibility measurements indicate that polymers 1-2 display antiferromagnetic exchange properties.

  10. 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.

  11. Novel lanthanide coordination polymers with a flexible disulfoxide ligand, 1,2-bis(ethylsulfinyl)ethane: structures, stereochemistry, and the influences of counteranions on the framework formations.

    PubMed

    Li, Jian-Rong; Bu, Xian-He; Zhang, Ruo-Hua

    2004-01-12

    The reactions of meso-1,2-bis(ethylsulfinyl)ethane (meso-L) with Ln(ClO(4))(3) [Ln(NO(3))(3) or Ln(NCS)(3)] in MeOH and CHCl(3) gave a series of new lanthanide coordination polymers, [[Ln(micro-meso-L)(rac-L)(2)(CH(3)OH)(2)](ClO(4))(3)](n) [Ln: La (1), Nd (2), Eu (3), Gd (4), Tb (5), Dy (6), and Yb (7)], [Yb(micro-meso-L)(1.5)(NO(3))(3)](n) (8), and [La(micro-meso-L)(2.5)(NCS)(3)](n) (9). All the structures were established by single-crystal X-ray diffraction. Complexes 1-7 are isostructural with infinite single micro-chain structure, in which the L ligands take two kinds of coordination modes: bidentate chelating and bis-monodentate bridging. Six sulfur atoms of the sulfoxide groups around each Ln(III) center adopt alternatively the same R or S configuration in the chain. In addition, the configuration change of partial ligands occurred from the meso to the rac form when reacting with Ln(ClO(4))(3). To our knowledge, this is the first example of disulfoxide complexes with two kinds of coordination modes and three kinds of configurations (R,R, S,S, and R,S) occurring simultaneously in the same complex. 8 exhibits single-double bridging chain structure, in which dinuclear macrometallacycles formed through bridging two Yb(III) by two meso-L ligands are further linked by another meso-L ligand. In 9 each La(III) ion is linked to five other La(III) ions by five meso-L ligands to form a 5-connected 2-D (3/4,5) network containing two types of macrometallacyclic arrays: quadrilateral and triangle grids. The structural differences among 1-7, 8, and 9 show that counteranions play important roles in the framework formation of such coordination polymers. In addition, the luminescent properties of 3 and 5 were also investigated.

  12. Preparation and characterization of organotin-oxomolybdate coordination polymers and their use in sulfoxidation catalysis.

    PubMed

    Abrantes, Marta; Valente, Anabela A; Pillinger, Martyn; Gonçalves, Isabel S; Rocha, João; Romão, Carlos C

    2003-06-16

    The organotin-oxomolybdates [(R(3)Sn)(2)MoO(4)].n H(2)O (R=methyl, n-butyl, cyclohexyl, phenyl, benzyl) have been prepared and tested as catalysts for the oxidation of benzothiophene with aqueous hydrogen peroxide, at 35 degrees C and atmospheric pressure. In all cases, the 1,1-dioxide was the only observed product. The kinetic profiles depend on the nature of the tin-bound R group and also on the addition of a co-solvent. For the tribenzyltin derivative, the apparent activation energies for sulfoxidation as a function of the co-solvent are in the order 1,2-dichloroethane (5 kcal mol(-1))polymers also have different structures, as evidenced by Xray powder diffraction. Mo K-edge and Sn K-edge EXAFS spectroscopy confirmed that the structures arise from the self-assembly of tetrahedral [MoO(4)](2-) subunits and [R(3)Sn](+) spacers. The Mo...Sn separation in the trimethyltin derivative is a uniform 3.84 A. By contrast, the EXAFS results revealed the coexistence of short (3.67-3.79 A) and long (3.93-4.07 A) Mo.Sn separations in the other coordination polymers. The catalyst precursors were also characterized in the solid state by thermogravimetric analysis, FTIR, and Raman spectroscopy, and MAS NMR ((13)C, (119)Sn) spectroscopy.

  13. Synthesis, spectral, X-ray diffraction and thermal studies of new ZnII-pyrazine coordination polymers

    NASA Astrophysics Data System (ADS)

    Marandi, Farzin

    2014-02-01

    Two new zinc(II) coordination polymers with a β-diketone and N-donor ancillary ligands, [Zn(pyz)(ttfa)2]n (1) and [Zn(pyz)(btfa)2]n (2), (Httfa = 2-thenoyltrifluoroacetone, Hbtfa = benzoyltrifluoroacetone and pyz = pyrazine), have been prepared and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy, and studied by thermal gravimetric analysis as well as single crystal X-ray diffraction. The crystal and molecular structures of 1 and 2 have been solved by X-ray diffraction and they turned out to be one-dimensional polymers with linear dispositions of the metal atoms. These one-dimensional polymers are further connected to form a 3D supramolecular network by CH⋯π (only in 1), CH⋯F, π-π and interesting H⋯H (only in 2) interactions.

  14. Dendronized organoplatinum(II) metallacyclic polymers constructed by hierarchical coordination-driven self-assembly and hydrogen-bonding interfaces.

    PubMed

    Yan, Xuzhou; Jiang, Bo; Cook, Timothy R; Zhang, Yanyan; Li, Jinying; Yu, Yihua; Huang, Feihe; Yang, Hai-Bo; Stang, Peter J

    2013-11-13

    We describe the efficient preparation of rhomboidal metallacycles that self-assemble upon mixing a donor decorated with 2-ureido-4-pyrimidinone (UPy) with acceptors containing pendant [G1]-[G3] dendrons. The formed rhomboids subsequently polymerize into dendronized organoplatinum(II) metallacyclic polymers through H-bonding UPy interfaces, which possess the structural features of conventional dendronized polymers as well as the dynamic reversibility of supramolecular polymers. Preservation of both properties in a single material is achieved by exploiting hierarchical self-assembly, namely the unification of coordination-driven self-assembly with H-bonding, which provides facile routes to dendronized metallacycles and subsequent high ordering. The supramolecular polymerization defined here represents a novel method to deliver architecturally complex and ordered polymeric materials with adaptive properties.

  15. Syntheses, structures and luminescent properties of a series of 3D lanthanide coordination polymers with tripodal semirigid ligand

    SciTech Connect

    Qin Junsheng; Du Dongying; Chen Lei; Sun Xiuyun; Lan Yaqian; Su Zhongmin

    2011-02-15

    Reactions of the tripodal bridging ligand 5-(4-carboxy-phenoxy)-isophthalic acid (abbreviated as H{sub 3}cpia) with lanthanide salts lead to the formation of a family of different coordination polymers, that is, [Ln(cpia)(H{sub 2}O){sub 2}]{sub n}.nH{sub 2}O (Ln=Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Dy (7), Er (8), Tm (9) and Y (10)) in the presence of formic acid or diethylamine, which are characterized by elemental analysis, IR spectrum, thermogravimetric analysis (TGA), XRPD spectrum and single-crystal X-ray diffraction. Compounds 1-10 are isostructural and exhibit three-dimensional microporous frameworks. Furthermore, the photoluminescent properties of 4, 5 and 7 have been studied in detail. -- Graphical abstract: Reactions of the tripodal bridging ligand (H{sub 3}cpia) with lanthanide ions lead to the formation of a series of coordination polymers in the presence of formic acid or diethylamine. Display Omitted Research Highlights: {yields} Ten new lanthanides-based coordination polymers (1-10) have been synthesized. {yields} 1-10 exhibit 3D (4,8)-connected fluorite topology networks with 1D channel parallel to the b-axis. {yields} Compounds 4, 5 and 7 exhibit characteristic luminescence of Sm{sup 3+}, Eu{sup 3+} and Dy{sup 3+} ions, respectively.

  16. Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

    PubMed

    Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2012-09-17

    Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

  17. Syntheses, structures and luminescence for zinc coordination polymers based on a multifunctional 4′-(3-carboxyphenyl)- 3,2′:6′,3″-terpyridine ligand

    SciTech Connect

    Cheng, Yue; Yang, Meng-Lin; Hu, Huai-Ming Xu, Bing; Wang, Xiaofang; Xue, Ganglin

    2016-07-15

    Six new coordination polymers, [ZnLCl]{sub n}(1), [ZnL{sub 2}]{sub n}·2nH{sub 2}O (2), [Zn{sub 2}L(o-bdc)(OH)]{sub n}·0.5nH{sub 2}O (3), [Zn{sub 2}L(m-bdc)(OH)]{sub n}·nH{sub 2}O (4), [Zn{sub 2}L{sub 2}(p-bdc) (H{sub 2}O){sub 2}]{sub n}·nH{sub 2}O (5), [Zn{sub 2}L(1,2,4-btc)(H{sub 2}O)]{sub n}(6), (HL=4′-(3-carboxyphenyl)- 3,2′:6′,3″-terpyridine, H{sub 2}(o-bdc)= benzene-1,2-dicarboxylic acid, H{sub 2}(m-bdc)= benzene-1,3-dicarboxylic acid, H{sub 2}(p-bdc)= benzene-1,4-dicarboxylic acid, H{sub 3}(1,2,4-btc)= benzene-1,2,4-tricarboxylic acid) have been synthesized under the hydrothermal conditions. Compound 1 displays a 3-connected 2D network structure with point symbol of {8"2.10}. Compound 2 exhibits 1D infinite loop chain structure. Compound 3 possesses a (3,8)-connected 3D framework composed of tetranuclear units with point symbol of {4"3}{sub 2}{4"6.6"1"8.8"4}. Compound 4 features a typical 2D hcb network based on tetranuclear zinc(II) units with point symbol of {4"4.6"2}. Compound 5 presents a classical two-fold penetration sql network with point symbol of {6"3}. Compound 6 can be seen as a (3,3,6)-connected 3D net with point symbol of {4"2.6"4.8"9}{4"2.6}{6"3}. The thermal stability and luminescent properties of compounds 1–6 in the solid state are discussed in detail. - Graphical abstract: Six new Zn(II) coordination polymers based on multicarboxylate and terpyridyl derivative ligands have synthesized under the hydrothermal conditions and the thermal stability and luminescence are discussed. Display Omitted.

  18. Pore design of two-dimensional coordination polymers toward selective adsorption.

    PubMed

    Hijikata, Yuh; Horike, Satoshi; Sugimoto, Masayuki; Inukai, Munehiro; Fukushima, Tomohiro; Kitagawa, Susumu

    2013-04-01

    We have synthesized four porous coordination polymers (PCPs) using Zn(2+), 4,4'-sulfonyldibenzoate (sdb), and four types of dinitrogen linker ligands, 1,4-diazabicyclo[2,2,2]octane (dabco), 1,4-bis(4-pyridyl)benzene (bpb), 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine (bpt), and 4,4'-bipyridyl (bpy). The bent sdb ligands form a rhombic space connected by zinc paddle-wheel units to form a one-dimensional double chain, and each dinitrogen ligand linked the one-dimensional double chains. There are different assembled structures of two-dimensional sheets with the same connectivities between Zn(2+) and the organic ligands. [Zn2(sdb)2(dabco)]n (1) has a noninterpenetrated and noninterdigitated structure, [Zn2(sdb)2(bpb)]n (2) and [Zn2(sdb)2(bpt)]n (3) have interdigitated structures, and [Zn2(sdb)2(bpy)]n (4) has an interpenetrated structure. The length of the dinitrogen ligands dominated their assembled structures and flexibility, which influence the adsorption properties. The flexible frameworks of 2 and 3 provide different stepwise adsorption behaviors for CO2, CH4, C2H6, and C2H4 affected by their pore diameters and the properties of the gases. Their different adsorption properties were revealed by IR spectroscopy and X-ray analysis under a gas atmosphere. The framework of 4 possesses less flexibility and a smaller void space than the others and a negligible amount of CH4 was adsorbed; however, 4 can adsorb either C2H6 or C2H4 through the gate-opening phenomenon. Measurement of the solid-state (2)H NMR was also carried out to investigate the relationship between the framework structure and the dynamics of bpy with regard to the lower flexibility of 4. We have demonstrated a strategy to control the pore size and assembled structures toward selective adsorption properties of PCPs.

  19. Synthesis of nanostructured materials by using metal-cyanide coordination polymers and their lithium storage properties.

    PubMed

    Nie, Ping; Shen, Laifa; Luo, Haifeng; Li, Hongsen; Xu, Guiyin; Zhang, Xiaogang

    2013-11-21

    Herein, we demonstrate a novel and simple two-step process for preparing LiCoO2 nanocrystals by using a Prussian blue analogue Co3[Co(CN)6]2 as a precursor. The resultant LiCoO2 nanoparticles possess single crystalline nature and good uniformity with an average size of ca. 360 nm. The unique nanostructure of LiCoO2 provides relatively shorter Li(+) diffusion pathways, thus facilitating the fast kinetics of electrochemical reactions. As a consequence, high reversible capacity, excellent cycling stability and rate capability are achieved with these nanocrystals as cathodes for lithium storage. The LiCoO2 nanocrystals deliver specific capacities of 154.5, 135.8, 119, and 100.3 mA h g(-1) at 0.2, 0.4, 1, and 2 C rates, respectively. Even at a high current density of 4 C, a reversible capacity of 87 mA h g(-1) could be maintained. Importantly, a capacity retention of 83.4% after 100 cycles is achieved at a constant discharge rate of 1 C. Furthermore, owing to facile control of the morphology and size of Prussian blue analogues by varying process parameters, as well as the tailored design of multi-component metal-cyanide hybrid coordination polymers, with which we have successfully prepared porous Fe2O3@NixCo3-xO4 nanocubes, one of the potential anode materials for lithium-ion batteries, such a simple and scalable approach could also be applied to the synthesis of other nanomaterials for energy storage devices.

  20. Nanoscale Mn(II) -Coordination Polymers for Cell Imaging and Heterogeneous Catalysis.

    PubMed

    Sarkar, Koushik; Dastidar, Parthasarathi

    2016-12-23

    A mixed ligand approach was exploited to synthesize a new series of Mn(II) -based coordination polymers (CPs), namely, CP1 {[Mn(μ-dpa)(μ-4,4'-bp)]⋅MeOH}∞ , CP2 {[Mn3 (μ-dpa)3 (2,2'-bp)2 ]}∞ , CP3 {[Mn3 (μ-dpa)3 (1,10-phen)2 ]⋅2 H2 O}∞ , CP4 {[Mn(μ-dpa)(μ-4,4'-bpe)1.5 ]⋅H2 O}∞ , CP5 {[Mn2 (μ-dpa)2 (μ-4,4'-bpe)2 ]⋅1/2  DEF}∞ , and CP6 {[Mn(μ-dpa)(μ-4,4'-bpe)1.5 ]⋅1/2  DMA}∞ (dpa=3,5-dicarboxyphenyl azide, 2,2'-bp=2,2'-bipyridine, 1,10-phen=1,10-phenanthroline, 4,4'-bpe=1,2-bis(4-pyridyl)ethylene, 4,4'-bp=4,4'-bipyridine, DEF=N,N-diethylformamide, DMA=N,N-dimethylacetamide), to develop multifunctional CPs. Various techniques, such as single-crystal X-ray diffraction (SXRD), FTIR spectroscopy, elemental analysis, and thermogravimetric analysis, were employed to fully characterize these CPs. The majority of the CPs displayed a four-connected sql topology, whereas CP4 and CP6 exhibited a two-dimensional SnS network architecture, which was further entangled in a polycatenation mode. Compound CP1 displayed an open framework structure. The CPs were scaled down to the nanoregime in a ball mill for cell imaging studies. Whereas CP2 and CP4 were employed for cell imaging with RAW264.7 cells, CP1 was exploited for both cell imaging and heterogeneous catalysis in a cyanosilylation reaction.

  1. Lanthanide contraction effect on crystal structures of lanthanide coordination polymers with cyclohexanocucurbit[6]uril ligand

    NASA Astrophysics Data System (ADS)

    Zheng, Li-Mei; Liu, Jing-Xin

    2017-01-01

    A series of compounds based on the macrocyclic ligand cyclohexanocucurbit[6]uril (Cy6Q[6]) with formulas {Ln(H2O)6Cy6Q[6]}·2(CdCl4)·H3O·xH2O [isomorphous with Ln=La (1), Ce (2), Pr (3) and Nd (4), x=11 (1), 11 (2), 10 (3) and 11 (4)], {Sm(H2O)5Cy6Q[6]}·2(CdCl4)·H3O·10H2O (5) and {Ln(H2O)5(NO3)@Cy6Q[6]}·2(CdCl4)·2H3O·xH2O [isomorphous with Ln=Gd (6), Tb (7) and Dy (8), x=8 (6), 6 (7) and 6 (8)], have been successfully synthesized by the self-assembly of Cy6Q[6] with the corresponding lanthanide nitrate under hydrochloric acid aqueous solution in the presence of CdCl2. Single-crystal X-ray diffraction analyses revealed that compounds 1-8 all crystallize in monoclinic space group P21/c, and display 1D coordination polymer structures. The lanthanide contraction effect on the structures of 1-8 has also been investigated and discussed in detail. In contrast, the reaction of Cy6Q[6] with the Ho(NO)3, Tm(NO)3, Yb(NO)3 under the same conditions resulted in the compounds 9-11 with formulas Cy6Q[6]·2(CdCl4)·2H3O·xH2O [isomorphous with x=10 (9), 10 (10), and 9 (11)], in which no lanthanide cations are observed. The structural difference of these compounds indicates that the Cy6Q[6] may be used in the separation of lanthanide cations.

  2. Role of polar side chains in Li(+) coordination and transport properties of polyoxetane-based polymer electrolytes.

    PubMed

    Sai, Ryansu; Ueno, Kazuhide; Fujii, Kenta; Nakano, Yohei; Shigaki, Naho; Tsutsumi, Hiromori

    2017-02-15

    Lithium ion conducting polymer electrolytes (PEs) have been the subject of intense research for lithium metal battery applications. Here, we investigate the effects of polar side chains on Li(+) coordination and ionic transport properties to gain insights for improving the insufficient conductivity of traditional ether-based solid PEs. Poly(trimethyleneoxide)-based (or polyoxetane-based) polymers with ether or nitrile groups were synthesized by ring-opening polymerization. The thermal, ionic transport, and electrochemical properties and the local structure of Li(+) coordination were studied in the presence of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA). The glass transition temperature (Tg) of the PEs with ether side chains increased with increasing LiTFSA content, whereas the PEs with the nitrile functionality showed the opposite trend at higher salt concentrations. In addition to the unique trend for the Tg values of the PEs in the presence of LiTFSA, the nitrile groups played pivotal roles as coordination sites for Li(+) ions in the first coordination shell and as a polar medium to increase the permittivity of the PEs. These characteristics of the nitrile groups can endow PEs with improved ionic transport properties.

  3. Self-Assembly of Tunable Heterometallic Ln-Ru Coordination Polymers with Near-Infrared Luminescence and Magnetocaloric Effect.

    PubMed

    Wang, Lei; Xie, Zhigang; Dang, Song; Sun, Zhong-Ming

    2017-02-24

    A series of heterometallic lanthanide (Ln)-Ru coordination polymers, denoted Gd-1, Yb-2, and Nd-3, were prepared by solvothermal reaction of a carboxylate derivative of [Ru(bpy)3 ](2+) (Rubpy, bpy=2,2'-bipyridine), oxalic acid, and Ln(OAc)3 by using the metalloligand strategy. Single-crystal X-ray diffraction indicated that the resulting isostructural heterometallic complexes have 1D butterfly-shaped Ln-Ru-based coordination chains but show slight differences in the coordination environments of the Ln centers. The introduced Ru(bpy) metalloligands could act as good light-harvesting antennas to effectively sensitize near-infrared (NIR) luminescence by energy transfer from the triplet metal-to ligand charge transfer state of Rubpy units to Ln (Yb or Nd) under the excitation in the visible-light region. Additionally, dopant-concentration-dependent behavior of the Ru-based emission and sensitized NIR emission was demonstrated in Gd-1. Finally, the magnetocaloric effect of Gd-1 was studied. The preparation of such heterometallic coordination polymers offers a versatile platform to investigate dimensionally controlled properties.

  4. Cadmium coordination polymers based on flexible bis(imidazole) ligands: A rare example for doublet of doublet cadmium polyhedron arrangements

    NASA Astrophysics Data System (ADS)

    Babu, Chatla Naga; Suresh, Paladugu; Sampath, Natarajan; Prabusankar, Ganesan

    2014-10-01

    Two one-dimensional (1D) coordination polymers, [{LCd(O2NO)2(DMF)2}2{(LCd(O2NO)2(DMF))(DMF)}2]n (1) and [L‧Cd(O2NO)(ONO2)(DMF)2]n (2), having an aryl chromophoric unit and a flexible bis(imidazole) tail, 9,10-bis{(benzimidazol)methyl}anthracene (L) and 1,4-bis{(imidazol)methyl}benzene (L‧), with various coordination modes have been obtained. Molecule 1 represents the first structurally characterized one dimensional coordination polymer consisting of both hepta- and octa-coordinated cadmium centers. In 1, two distorted pentagonal bipyramidal Cd(II) centers and two distorted triangular dodecahedral Cd(II) centers are alternately arranged via bridging bidentate N,N-chelating ligand, L. Whereas, a distorted pentagonal bipyramidal Cd(II) center is formed in 2 where the sterically less crowded L‧ serves as a bridging bidentate N,N-chelating ligand. Furthermore, 1 and 2 have been characterized by elemental analysis, FT-IR, 1H NMR, UV-vis and fluorescent techniques.

  5. Synthesis, crystal structure, and magnetic properties of two-dimensional divalent metal glutarate/dipyridylamine coordination polymers, with a single crystal-to-single crystal transformation in the copper derivative

    SciTech Connect

    Montney, Matthew R.; Supkowski, Ronald M.; Staples, Richard J.; LaDuca, Robert L.

    2009-01-15

    Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4'-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a '5+1' extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)]{sub n} neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure of 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses. - Graphical abstract: The coordination polymers [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)]{sub n} chains linked through dpa tethers. Antiferromagnetic coupling is observed for 2 and 3, while ferromagnetism is predominant in 1. Compound 3 undergoes a thermally induced single crystal-to-single crystal transformation from an acentric to a centrosymmetric space group.

  6. 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.

  7. Complexations of Ln(III) with SnS4H and Sn2S6: Solvothermal syntheses and characterizations of lanthanide coordination polymers with thiostannate and polyamine mixed ligands

    NASA Astrophysics Data System (ADS)

    Tang, Chunying; Lu, Jialin; Han, Jingyu; Liu, Yun; Shen, Yali; Jia, Dingxian

    2015-10-01

    Polymeric lanthanide complexes with thiostannate and polyamine mixed ligands, [Ln(peha)(μ-SnS4H)]n [Ln=La (1a), Nd (1b)] and [{Ln(tepa)(μ-OH)}2(μ-Sn2S6)]nnH2O [Ln=Nd (2a), Sm (2b), Gd (2c), Dy (2d)] (peha=pentaethylenehexamine, tepa=tetraethylenepentamine) were respectively prepared in peha and tepa coordinative solvents by the solvothermal methods. In 1a and 1b, the Ln3+ ions are coordinated by a hexadentate peha ligand forming [Ln(peha)]3+ units. The [SnS4H]3- anion chelates a [Ln(peha)]3+ unit via two S atoms and coordinates to another [Ln(peha)]3+ unit via the third S atom. As a result, the [Ln(peha)]3+ units are connected into coordination polymers [Ln(peha)(μ-SnS4H)]n by an unprecedented tridentate μ-η1,η2-SnS4H bridging ligands. In 2a-2d, the Ln3+ ions are coordinated by a pentadentate tepa ligand, and two [Ln(tepa)]3+ units are joined by two μ-OH bridges to form a binuclear [{Ln(tepa)(μ-OH)}2]4+ unit. Behaving as a bidentate μ-η1, η1-Sn2S6 bridging ligand, the Sn2S6 unit connects [{Ln(tepa)(μ-OH)}2]4+ units into a neutral coordination polymer [{Ln(tepa)(μ-OH)}2(μ-Sn2S6)]n via the trans S atoms. The Ln3+ ions are in distorted monocapped square antiprismatic and bicapped trigonal prismatic environments in [{Ln(peha)(μ-SnS4H)]n and [{Ln(tepa)(μ-OH)}2(μ-Sn2S6)]n, respectively. The denticities of ethylene polyamine play an important role on the formation and complexation of the thiostannate in the presence of lanthanide ions. Compounds 1a-2d show well-defined absorption edges with band gaps between 2.81 and 3.15 eV.

  8. Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

    SciTech Connect

    Lin, Hong-Yan; Lu, Huizhe; Le, Mao; Luan, Jian; Wang, Xiu-Li; Liu, Guocheng; Zhang, Juwen

    2015-03-15

    Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){sub 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8

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

    SciTech Connect

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

    2016-01-15

    Two novel coordination polymers, namely, [Ca(NCP){sub 2}]{sub ∞} (I) and [Sr(NCP){sub 2}]{sub ∞} (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{sup −}){sub 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{sup −} which stabilize the frameworks. Both I and II display stronger fluorescence emissions as well as high thermal stability. - Graphical abstract: One-dimensional nanotubular channels with the cross dimension of 37.1959(20)×23.6141(11)Å{sup 2} in the three-dimensional honeycomb-shaped coordination network of II are observed. The topological analysis of II indicates that there exists a typical diamond framework possessing large adamantanoid cages, which containing four cyclohexane-shaped patterns in chair conformations. - Highlights: • Two isomorphous and isostructural coordination polymers based on flexible ligand and two alkaline-earth metal salts have been synthesized and characterized. • Structural analysis indicates that I and II are assembled into 3D porous honeycomb-shaped metal-organic frameworks. • Both I and II display stronger fluorescence emissions and higher thermal stability.

  10. Heterometallic Coordination Polymers Assembled from Trigonal Trinuclear Fe2Ni-Pivalate Blocks and Polypyridine Spacers: Topological Diversity, Sorption, and Catalytic Properties.

    PubMed

    Sotnik, Svetlana A; Polunin, Ruslan A; Kiskin, Mikhail A; Kirillov, Alexander M; Dorofeeva, Victoria N; Gavrilenko, Konstantin S; Eremenko, Igor L; Novotortsev, Vladimir M; Kolotilov, Sergey V

    2015-06-01

    Linkage of the trigonal complex [Fe2NiO(Piv)6] (where Piv(-) = pivalate) by a series of polypyridine ligands, namely, tris(4-pyridyl)triazine (L(2)), 2,6-bis(3-pyridyl)-4-(4-pyridyl)pyridine (L(3)), N-(bis-2,2-(4-pyridyloxymethyl)-3-(4-pyridyloxy)propyl))pyridone-4 (L(4)), and 4-(N,N-diethylamino)phenyl-bis-2,6-(4-pyridyl)pyridine (L(5)) resulted in the formation of novel coordination polymers [Fe2NiO(Piv)6(L(2))]n (2), [Fe2NiO(Piv)6(L(3))]n (3), [Fe2NiO(Piv)6(L(4))]n·nHPiv (4), and [{Fe2NiO(Piv)6}4{L(5)}6]n·3nDEF (5, where DEF is N,N-diethylformamide), which were crystallographically characterized. The topological analysis of 3, 4, and 5 disclosed the 3,3,4,4-connected 2D (3, 4) or 3,4,4-connected 1D (5) underlying networks which, upon further simplification, gave rise to the uninodal 3-connected nets with the respective fes (3, 4) or SP 1-periodic net (4,4)(0,2) (5) topologies, driven by the cluster [Fe2Ni(μ3-O)(μ-Piv)6] nodes and the polypyridine μ3-L(3,4) or μ2-L(5) blocks. The obtained topologies were compared with those identified in other closely related derivatives [Fe2NiO(Piv)6(L(1))]n (1) and {Fe2NiO(Piv)6}8{L(6)}12 (6), where L(1) and L(6) are tris(4-pyridyl)pyridine and 4-(N,N-dimethylamino)phenyl-bis-2,6-(4-pyridyl)pyridine, respectively. It was shown that a key structure-driven role in defining the dimensionality and topology of the resulting coordination network is played by the type of polypyridine spacer. Compounds 2 and 3 possess a porous structure, as confirmed by the N2 and H2 sorption data at 78 K. Methanol and ethanol sorption by 2 was also studied indicating that the pores filled by these substrates did not induce any structural rearrangement of this sorbent. Additionally, porous coordination polymer 2 was also applied as a heterogeneous catalyst for the condensation of salicylaldehyde or 9-anthracenecarbaldehyde with malononitrile. The best activity of 2 was observed in the case of salicylaldehyde substrate, resulting in up to 88

  11. Construction of five Zn(ii)/Cd(ii) coordination polymers derived from a new linear carboxylate/pyridyl ligand: design, synthesis, and photocatalytic properties.

    PubMed

    Liu, Lei-Lei; Yu, Cai-Xia; Du, Ji-Min; Liu, Shi-Min; Cao, Jing-Shuai; Ma, Lu-Fang

    2016-08-02

    Solvothermal reactions of Cd(OAc)2/Zn(OAc)2 with a new ligand, (pyridin-3-yl)methyl 4-(2-(4-((pyridin-3-yl)methoxy)phenyl)diazenyl)benzoate (L1), under different templates via an in situ ligand transformation reaction produced five coordination polymers, [CdL2(H2O)]n (1), [Cd1.5L3]n (2), [Cd2L4]n (3), [(ZnL2)·H2O]n (4) and {[Zn(1,3-BDC)(L1)]·MeCN·0.5H2O}n (5), where HL = 4-(2-(4-((pyridin-3-yl)methoxy)phenyl)diazenyl)benzoic acid, 1,3-H2BDC = 1,3-benzenedicarboxylic acid. Compound 1 is a three-dimensional (3D) wave-like structure constructed from 4-connected Cd(ii) nodes and L(-) linkers. Compounds 2 and 3 bear similar 2D networks built from metallocyclic [Cd4L4] units. Compound 4 features a wrinkled 2D layer based on metallocyclic [Zn4L4] units. Compound 5 has a novel 1D single-wall metal-organic nanotube (SWMONT) in which the 1,3-BDC ligands act as linkers to connect the [Zn2(L1)2] rings. The results reveal that the different templates have a significant effect on the final structures. Compounds 1-5 exhibited relatively high photocatalytic activity towards the degradation of methylene blue (MB) in aqueous solution under UV-Vis irradiation. The kinetics of the catalytic photodegradation reactions and the stabilities of photocatalysts were also investigated.

  12. Assemblies of a new flexible multicarboxylate ligand and d10 metal centers toward the construction of homochiral helical coordination polymers: structures, luminescence, and NLO-active properties.

    PubMed

    Zang, Shuangquan; Su, Yang; Li, Yizhi; Ni, Zhaoping; Meng, Qingjin

    2006-01-09

    Hydro(solvo)thermal reactions between a new flexible multicarboxylate ligand of 2,2',3,3'-oxydiphthalic acid (2,2',3,3'-H(4)ODPA) and M(NO(3))(2).xH(2)O (M = Zn, x = 6; M = Cd, x = 4) in the presence of 4,4'-bipyridine (bpy) afford two novel homochiral helical coordination polymers [[Zn(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 1 and [Cd(2)(2,2',3,3'-ODPA)(bpy)(H(2)O)(3)].(H(2)O)(2) for 2]. Though having almost the same chemical formula, they have different space groups (P2(1)2(1)2(1) for 1 and P2(1) for 2) and different bridging modes of the 2,2',3,3'-ODPA ligand. Two kinds of homochiral helices (right-handed) are found in both 1 and 2, each of which discriminates only one kind of crystallographical nonequivalent metal atom. 1 has a 2D metal-organic framework and can be seen as the unity of two parallel homochiral Zn1 and Zn2 helices, in which the nodes are etheric oxygen atoms. In contrast, 2 has a 3D metal-organic framework and consists of two partially overlapped homochiral Cd1 and Cd2 helices in the two dimensions. Moreover, metal-ODPA helices give a 2D chiral herringbone structural motif in both 1 and 2 in the two dimensions, which are further strengthened by the second ligand of bpy. Bulk materials for 1 and 2 all have good second-harmonic generation activity, approximately 1 and 0.8 times that of urea.

  13. 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.

  14. Hydrogen-bonded porous coordination polymers: structural transformation, sorption properties, and particle size from kinetic studies.

    PubMed

    Uemura, Kazuhiro; Saito, Kazuya; Kitagawa, Susumu; Kita, Hidetoshi

    2006-12-20

    Three new coordination polymers, [CoCl2(4-pmna)2]n (1), {[Co(NCS)2(4-pmna)2].2Me2CO}n (2 superset 2Me2CO), and {[Co(4-pmna)2(H2O)2](NO3)2.2CH3OH}n (3 superset 2H2O.2MeOH) (4-pmna = N-(pyridin-4-ylmethyl)nicotinamide), have been synthesized and characterized using single-crystal X-ray diffraction. The cobalt(II) atoms are bridged by 4-pmna ligands in all three compounds to form double-stranded one-dimensional "repeated rhomboid-type" chains with rectangular-shaped cavities. In 1, each chain slips and obstructs the neighboring cavities so that there are no guest-incorporated pores. Both 2 superset 2Me2CO and 3 superset 2H2O.2MeOH do not have such a staggered arrangement and have pores that can be filled with a guest molecule. Compound 3 superset 2H2O.2MeOH traps guest molecules with multiple hydrogen bonds and shows a reversible structural rearrangement during adsorption and desorption. The new crystalline compound, 3, is stabilized by forming hydrogen bonds with the amide moieties of the 4-pmna ligands and was characterized using infrared spectroscopy. The clathration enthalpy of the reaction 3 + 2H2O(l) + 2MeOH(l) <==> 3 superset 2H2O.2MeOH (approximately 35 kJ/mol) was estimated from differential scanning calorimetry data by considering the vaporization enthalpies of H2O and MeOH. The desorption process of 3 superset 2H2O.2MeOH --> 3 follows a single zero-order reaction mechanism under isothermal conditions. The activation energy of ca. 100 kJ/mol was obtained by plotting the logarithm of the reaction time for the same reacted fraction versus the reciprocal of the temperature. Moreover, the distribution of the one-dimensional channels in 3 superset 2H2O.2MeOH was estimated using the observation that the reaction rate is directly proportional to the total sectional area.

  15. Bottom-up synthesis of three heterometallic coordination polymers with layered structures constructed from presynthesized [Sb 2(tart) 2] 2- metalloligands

    NASA Astrophysics Data System (ADS)

    Zhang, Guang-Ju; Xiao, Dong-Rong; Sun, Dian-Zhen; Chen, Hai-Yan; He, Jiang-Hong; Yuan, Ruo; Wang, En-Bo

    2012-01-01

    Self-assembly of presynthesized [Sb 2(tart) 2] 2- metalloligand as molecular building block with metal salts affords three unique heterometallic coordination polymers, namely, {[Ln(H 2O) 6][Sb 2(tart) 2]}Cl·5H 2O (Ln = La ( 1), Pr ( 2)) and {[Ba 2(H 2O) 7][Sb 2(tart) 2] 2}·4H 2O ( 3), (tart = tartaric acid). Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and TG analyses. Compounds 1 and 2 are isostructural and represent the first examples of lanthanide-organic open frameworks containing [Sb 2(tart) 2] 2- metalloligands. The structures of 1 and 2 contain left-handed and right-handed layer, each built up from the same-handed helical chains. Compound 3 consists of two kinds of arm-shaped chiral layers, which alternately stack in a heterochiral fashion to yield a racemic 3D hydrogen-bonded network with 1D channels along the a axis. To the best of our knowledge, compounds 1- 3 are the first 2D chiral layer frameworks constructed from [Sb 2(tart) 2] 2- metalloligands and rare-earth or alkaline-earth metal ions.

  16. From racemic compound to spontaneous resolution: A series of homochiral lanthanide coordination polymers constructed from presynthesized [Sb2(tart)2]2- metalloligands

    NASA Astrophysics Data System (ADS)

    He, Jianghong; Zhang, Guangju; Xiao, Dongrong; Chen, Haiyan; Yan, Shiwei; Wang, Xin; Yang, Juan; Yuan, Ruo; Wang, Enbo

    2012-06-01

    A series of homochiral 1D lanthanide coordination polymers, namely {Ln(H2O)5(NO3)[Sb2(D-tart)2]}·H2O (Ln = Ce (1), Eu (5)) and {Ln(H2O)5(NO3)[Sb2(L-tart)2]}·H2O (Ln = Pr (2), Nd (3), Sm (4), Dy (6)) (tart = tartaric acid) were obtained by spontaneous resolution from presynthesized racemic [Sb2(tart)2]2- metalloligands (MLs). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, X-ray powder diffraction, and TG analyses. Compounds 1-6 are isostructural and feature novel 1D homochiral chains. There are three types of hydrogen-bonded helices in the 3D supramolecular network of 1-6. This case is still rare in metal-organic complexes. In addition, the luminescent properties of 4-6 were studied in the solid state at room temperature.

  17. Highly efficient electrochemiluminescence based on 4-amino-1,2,4-triazole Schiff base two-dimensional Zn/Cd coordination polymers.

    PubMed

    Zhang, Shu-Hua; Wang, Ji-Ming; Zhang, Hai-Yang; Fan, Yi-Peng; Xiao, Yu

    2017-01-03

    Four coordination polymers, formulated as [Zn(L(1))2]n (1), [Cd(L(1))2]n (2), [Zn(L(2))2]n (3) and [Cd(L(2))2]n (4) (HL1 is (E)-2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dibromophenol; HL2 is (E)-2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dichlorophenol) have been synthesized through vial reactions. The four compounds were structurally characterized by single crystal X-ray diffraction, elemental analysis, PXRD, and fluorescence spectroscopy. For 1-4, a detailed analysis of Hirshfeld surfaces and fingerprint plots facilitates a comparison of intermolecular interactions, which are crucial in building different supramolecular architectures. C-HX (X = Br, Cl) interactions play a crucial role in stabilizing the self-assembly process among adjacent 2-D networks for both complexes. Above all, complexes 1-4 showed highly intense electrochemical luminescence (ECL) in DMF solution and high thermal stability.

  18. Diverse assemblies of the (4,4) grid layers exemplified in Zn(II)/Co(II) coordination polymers with dual linear ligands

    NASA Astrophysics Data System (ADS)

    Liu, Guang-Zhen; Li, Xiao-Dong; Xin, Ling-Yun; Li, Xiao-Ling; Wang, Li-Ya

    2013-07-01

    Diverse (4,4) grid layers are exemplified in five two-dimensional coordination polymers with dual μ2-bridged ligands, namely, {[Zn(cbaa)(bpp)]·H2O}n (1), [Zn2(cbaa)2(bpy)]n (2), [Co2(cbaa)2(bpp)2]n (3), [Co(cbaa)(bpp)]n (4), and [Co(bdaa)(bpp)(H2O)2]n (5) (H2cbaa=4-carboxybenzeneacetic acid, bpp=1,3-di(4-pyridyl)propane, bpy=4,4‧-bipyridyl, and H2bdaa=1,4-benzenediacrylic acid). For 1, two (4,4) grid layers with [ZnN2O2] tetrahedron as the node are held together by lattice water forming a H-bonding bilayer. Individual (4,4) grid layer in 2 is based on {Zn2(OCO)4} paddlewheel unit as the node. Two (4,4) grid layers with {Co2O(OCO)2} dimer as the node are covalently interconnected by organic ligands affording a thick bilayer of 3 with new framework topology. The different entanglements between two coincident (4,4) grid layers with [CoN2O4] octahedron as the node leads to two 2D→2D interpenetrated structures for 4 and 5. Furthermore, fluorescent properties of 1 and 2 as well as magnetic properties of 3 are investigated.

  19. A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

    SciTech Connect

    Wang, Jin-Hua; Tang, Gui-Mei; Qin, Ting-Xiao; Yan, Shi-Chen; Wang, Yong-Tao; Cui, Yue-Zhi; Weng Ng, Seik

    2014-11-15

    Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11 nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one

  20. MIL-HDBK-17 Polymer Matrix Composites Coordination Group Meeting (29th) Held in Monterey, California on March 29-31, 1994

    DTIC Science & Technology

    1994-03-31

    AD-A279 917 MIL-HDBK-1 7 POLYMER MATRIX COMPOSITES COORDINATION GROUP Twenty-Ninth Meeting 29 - 31 March, 1994 Monterey, CA DTIC ELECTE JUN 0 11994...QUAL PROCEEDINGS OF THE TWENTY-NINTH MIL-HDBK-17 COORDINATION GROUP MEETING MONTEREY, CALIFORNIA 29 - 31 MARCH 1994 TABLE OF CONTENTS Page 1. MIL-HDBK...17 COORDINATION GROUP MINUTES .................... 2 2. WORKING GROUP REPORTS .................................. 5 Braiding

  1. 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.

  2. Syntheses, structures, and photoluminescent properties of two silver (I) coordination polymers with 1, 4-bis(imidazol-1-ylmethyl) benzene

    NASA Astrophysics Data System (ADS)

    Wang, Zhan-Hui; Chen, Shu-Fen; Wang, Dan-Feng; Hao, Hong-Jun; Mei, Hong-Xin; Huang, Rong-Bin; Zheng, Lan-Sun

    2013-10-01

    The ultrasonic reactions of Ag2O with 1, 4-bis(imidazol-1-ylmethyl) benzene (bix) and ancillary carboxylate ligands under the ammoniacal condition lead to two new coordination compounds, namely [Ag4(bix)4(pma)·(H2O)18]n(1) and [Ag(bix)(onb)·H2O]n(2)(H4pma = pyromellitic acid, Honb = o-nitrobenzoic acid). Both of the complexes have been characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. In complex 1, the Ag-bix 1D chains are connected with the 2D nets containing [Ag4(bix)2(pma)2] to form a 3D framework by Ag⋯Ag interaction. In complex 2, the coordination bonds link Ag(I) ions and bix ligands to form 1D chains which are extended into a 2D layer by inter-chain hydrogen bonds. The Ag⋯Ag interaction is also observed in 2. Moreover, the photoluminescence properties of the complexes were also investigated in the solid state at room temperature.

  3. Two dimensional cyano-bridged hetero-metallic coordination polymers containing metal⋅⋅⋅π interactions.

    PubMed

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

    2014-01-01

    Three cyano bridged hetero-metallic complexes of general formula, [Cu(NH3)2(μ-ampy)M(μ-CN)2(CN)2]n [ampy=4-aminomethylpyridine, M=Ni(II) (1), Pd(II) (2) and Pt(II) (3)] have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The complexes crystallize in triclinic system with space group P-1. In all complexes, M(II) ions are coordinated by four cyano ligands, and four N atoms in the equatorial plane around the Cu atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the cyanide N atoms in the axial positions. In one-dimensional structures of all the complexes, [Cu(ampy)](2+) cations and [M(CN)4](2-) anions are linked via bridging cyano ligands. The adjacent one-dimensional structures form a 2D network to connect by the μ-ampy bridging ligands. The 2D layers are further linked by metal⋯π and hydrogen bonding interactions to generate a three dimensional network.

  4. Fe-nitrilotriacetic acid coordination polymer nanowires: an effective sensing platform for fluorescence-enhanced nucleic acid detection

    NASA Astrophysics Data System (ADS)

    Zhou, Yunchun; Liu, Qian; Sun, Xuping; Kong, Rongmei

    2017-02-01

    The determination of specific nucleic acid sequences is key in identifying disease-causing pathogens and genetic diseases. In this paper we report the utilization of Fe-nitrilotriacetic acid coordination polymer nanowires as an effective nanoquencher for fluorescence-enhanced nucleic acid detection. The detection is fast and the whole process can be completed within 15 min. This nanosensor shows a low detection limit of 0.2 nM with selectivity down to single-base mismatch. This work provides us with an attractive sensing platform for applications.

  5. 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.

  6. Solvent induced synthesis, structure and properties of coordination polymers based on 5-hydroxyisophthalic acid as linker and 1,10-phenanthroline as auxiliary ligand

    SciTech Connect

    Kariem, Mukaddus; Yawer, Mohd; Sheikh, Haq Nawaz

    2015-11-15

    Three new coordination polymers [Mn(hip)(phen) (H{sub 2}O)]{sub n} (1), [Co(hip)(phen) (H{sub 2}O)]{sub n} (2), and [Cd(hip) (phen) (H{sub 2}O)]{sub n} (3) (H{sub 2}hip=5-hydroxyisophthalic acid; phen=1,10-phenanthroline) have been synthesized by solvo-hydrothermal method using diethyl formamide-water (DEF-H{sub 2}O) 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. - Graphical abstract: 1D helical chains of coordination polymers were synthesized by solvo-hydrothermal reaction of 5-hydroxyisopthalic acid and 1,10-phenanthroline with MnCl{sub 2}·4H{sub 2}O / CoCl{sub 2}·6H{sub 2}O / Cd(NO{sub 3}){sub 2}·6H{sub 2}O. - Highlights: • Solvent induced synthesis of three coordination polymers with 1D zig-zag structure. • Crystal structures of coordination polymers are reported and discussed. • 1,10-Phenanthroline influences magnetic and luminescent properties of polymers. • Coordination polymer of Cd is luminescent exhibiting large Stokes shift.

  7. Two Gd(III) coordination polymers based on a flexible tricarboxylate: Syntheses, structures, luminescence and catalytic properties

    NASA Astrophysics Data System (ADS)

    Zhu, Yu; Zhu, Min; Liu, Pan; Xia, Li; Wu, Yunlong; Xie, Jimin

    2017-02-01

    Two Gadolinium coordination polymers {[Gd·(TTTA)·(H2O)2]·2H2O}n (1) and [Gd·(TTTA)·DMF]n (2) have been synthesized based on Gd(NO3)3·6H2O and the flexible tripodal ligand 2,2‧,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H3TTTA) under hydrothermal conditions. In the structure of 1, the tridentate TTTA3- ligands connect the dimeric metal centers into an infinite one dimensional chain. While 2 shows a two dimensional network with tridentate TTTA3- ligands. The two complexes all quench the emission spectra after coordinated to the Gd3+ ions. The catalytic results indicate that two complexes show excellent activities for the cyanosilylation of benzaldehyde and its derivatives. Besides, 2 is better than 1 in the catalytic reactions due to more possibility of metal open sites.

  8. Encapsulating Mobile Proton Carriers into Structural Defects in Coordination Polymer Crystals: High Anhydrous Proton Conduction and Fuel Cell Application.

    PubMed

    Inukai, Munehiro; Horike, Satoshi; Itakura, Tomoya; Shinozaki, Ryota; Ogiwara, Naoki; Umeyama, Daiki; Nagarkar, Sanjog; Nishiyama, Yusuke; Malon, Michal; Hayashi, Akari; Ohhara, Takashi; Kiyanagi, Ryoji; Kitagawa, Susumu

    2016-07-13

    We describe the encapsulation of mobile proton carriers into defect sites in nonporous coordination polymers (CPs). The proton carriers were encapsulated with high mobility and provided high proton conductivity at 150 °C under anhydrous conditions. The high proton conductivity and nonporous nature of the CP allowed its application as an electrolyte in a fuel cell. The defects and mobile proton carriers were investigated using solid-state NMR, XAFS, XRD, and ICP-AES/EA. On the basis of these analyses, we concluded that the defect sites provide space for mobile uncoordinated H3PO4, H2PO4(-), and H2O. These mobile carriers play a key role in expanding the proton-hopping path and promoting the mobility of protons in the coordination framework, leading to high proton conductivity and fuel cell power generation.

  9. Mössbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy)2[Pd(CN)4

    NASA Astrophysics Data System (ADS)

    Kitazawa, Takafumi; Sekiya, Madoka; Kawasaki, Takeshi; Takahashi, Masashi

    2016-12-01

    57Fe Mössbauer spectroscopic results on the alternatively prepared spin crossover coordination polymer Fe(3-Clpy)2Pd(CN)4 sample I agree with those of SQUID data. Mössbauer specrum at RT shows two diffrent doublets which correspond to the HS1(inner doublet) and HS2(outer doublet). The intensity of the HS1 doublet decreases on cooling to 78 K at the expense of a new one featuring the LS singlet. Almost 100 % of HS1 change to LS singlet due to iron(II) ions coordinated by four N atoms of cyano groups and two N atoms of 3-Clpy ligand in the sample I. The SQUID data of the sample I prepared by a new direct contact method are different from those of the already reported Fe(3-Clpy)2Pd(CN)4 sample. The differences of the SQUID data are associated with particle size effects in molecule spin crossover samples.

  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. 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.

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

    DOE PAGES

    Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.; ...

    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.

  13. 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.

  14. 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.

  15. Synthesis and structural characterization of three copper coordination polymers with pyridine derivatives from hydro(solvo)thermal in situ decarboxylation reactions of 2,5-dicarboxylpyridine

    SciTech Connect

    Hou Qin; Xu Jianing; Yu Jiehui; Wang Tiegang; Yang Qingfeng; Xu Jiqing

    2010-07-15

    The hydro(solvo)thermal self-assembles of CuI, KI and 2,5-dicarboxylpyridine [2,5-(COOH){sub 2}py] in different molar ratios in H{sub 2}O/alcohol solutions produced three Cu coordination polymers as 2-D [N-C{sub 2}H{sub 5}py][Cu{sub 3}I{sub 4}] 1, 1-D [N-CH{sub 3}py][Cu{sub 2}I{sub 3}] 2 as well as 1-D [Cu(2-COOpy){sub 2}]{center_dot}H{sub 2}O 3 (N-C{sub 2}H{sub 5}py=N-ethylpyridine, N-CH{sub 3}py=N-methylpyridine, 2-COOpy=2-carboxylpyridine). N-C{sub 2}H{sub 5}py in 1 and N-CH{sub 3}py in 2 derived from the solvothermal in situ simultaneous decarboxylation and N-alkylation reactions of 2,5-(COOH){sub 2}py. The semi-decarboxylation reaction of 2,5-(COOH){sub 2}py into 2-COOpy occurred in the preparation of 3. X-ray single-crystal analysis revealed that CuI is transformed into a 2-D [Cu{sub 3}I{sub 4}]{sup -} layer in compound 1 and a 1-D chain in compound 2, templated by [N-C{sub 2}H{sub 5}py]{sup +} and [N-CH{sub 3}py]{sup +}, respectively. Compound 3 is a divalent Cu compound. The Cu(II) centers with a 4+2 geometry are coordinated by {mu}{sub 3}-mode 2-COOpy ligands. All of the title compounds were characterized by CHN analysis, IR spectrum analysis and TG analysis. Compounds 1 and 2 exhibit fluorescence properties with the maximum emissions at 581 nm for 1 and 537 nm for 2. - Graphical abstract: Three compounds were obtained via in situ metal-ligand hydro(solvo)thermal reactions of 2,5-(cooh){sub 2}py with cui. Three types of in situ reactions occurred for 2,5-(cooh){sub 2}py: decarboxylation n-ethylated in 1, n-methylated in 2 and semi-decarboxylation in 3.

  16. Series of Hydrated Heterometallic Uranyl-Cobalt(II) Coordination Polymers with Aromatic Polycarboxylate Ligands: Formation of U═O-Co Bonding upon Dehydration Process.

    PubMed

    Falaise, Clément; Delille, Jason; Volkringer, Christophe; Vezin, Hervé; Rabu, Pierre; Loiseau, Thierry

    2016-10-06

    Five new heterometallic UO2(2+)-Co(2+) coordination polymers have been obtained by hydrothermal reactions of uranyl nitrate and metallic cobalt with aromatic polycarboxylic acids. Single-crystal X-ray diffraction reveals the formation of four 3D frameworks with the mellitate (noted mel) ligand and one 2D network with the isophthalate (noted iso) ligand. The compounds [(UO2(H2O))2Co(H2O)4(mel)]·4H2O (1), [UO2Co(H2O)4(H2mel)]·2H2O (2), and [(UO2(H2O))2Co(H2O)4(mel)] (4) consist of 3D frameworks built up from the connection of mellitate ligands and mononuclear metallic centers. These three compounds exhibit two types of geometry for the uranyl cation: pentagonal bipyramidal environment for 1 and 4, and hexagonal bipyramidal environment for 2. Using the mellitate ligand, the uranyl dinuclear unit is isolated in the compound [(UO2)2(OH)2(Co(H2O)4)2(mel)]·2H2O (3). Due to their 2D framework and the presence of uncoordinated cobalt(II) cations, the compound [(UO2)(iso)3][Co(H2O)6]·3(H2O) (5) is drastically different than the previous one. The thermal behavior of compounds 1, 2, and 3 has been studied by thermogravimetric analysis, X-ray thermodiffraction, and in situ infrared. By heating, the dehydration of compounds 1 and 2 promotes two structural transitions (1 → 1' and 2 → 2'). The crystal structures of [(UO2(H2O))2Co(H2O)2(mel)] (1') and [(UO2)Co(H2mel)] (2') were determined by single-crystal X-ray diffraction; each of them presents a heterometallic interaction between uranyl bond and the Co(II) center. Due to the rarely reported coordination environment for the cobalt center in compound 2' (square pyramidal configuration), the magnetic properties and EPR characterizations of the compounds 2 and 2' were also investigated.

  17. Alkyl group dependence on structure and magnetic properties in layered cobalt coordination polymers containing substituted glutarate ligands and 4,4'-bipyridine

    SciTech Connect

    Nettleman, Joseph H.; Supkowski, Ronald M.; LaDuca, Robert L.

    2010-02-15

    Five two-dimensional divalent cobalt coordination polymers containing 4,4'-bipyridine (bpy) and substituted or unsubstituted glutarate ligands have been prepared hydrothermally and structurally characterized by single-crystal X-ray diffraction. [Co(mg)(bpy)]{sub n} (1, mg=3-methylglutarate) forms a (4,4) rhomboid grid structure based on the connection of {l_brace}Co{sub 2}(CO{sub 2}){sub 2}{r_brace} dimeric units. Using the more sterically encumbered ligands 3,3-dimethylglutarate (dmg) and 3-ethyl, 3-methylglutarate (emg) generated {l_brace}[Co(dmg)(bpy)(H{sub 2}O)].2H{sub 2}O{r_brace}{sub n} (2) and {l_brace}[Co(emg)(bpy)(H{sub 2}O)].H{sub 2}O{r_brace}{sub n} (3), respectively. These complexes manifest {l_brace}Co(CO{sub 2}){r_brace}{sub n} chains linked into 2-D by aliphatic dicarboxylate and bpy ligands. The 'tied-back' substituted glutarate ligand 1,1-cyclopentanediacetate (cda) afforded [Co(cda)(bpy)]{sub n} (4), and the unsubstituted glutarate (glu) generated [Co(glu)(bpy)]{sub n} (5), both of which exhibit a topology similar to that of 1. The magnetic properties of complexes 1-4 were analyzed successfully with a recently developed phenomenological chain model accounting for both magnetic coupling (J) and zero-field splitting effects (D), even though 1 and 4 contain isolated, discrete {l_brace}Co{sub 2}(CO{sub 2}){sub 2}{r_brace} dimers. The D parameter in this series varied between 21.8(8) and 48.0(9) cm{sup -1}. However weak antiferromagnetic coupling was observed in 1 (J=-2.43(4) cm{sup -1}) and 4 (J=-0.89(2) cm{sup -1}), while weak ferromagnetic coupling appears to be operative in both 2 (J=0.324(5) cm{sup -1}) and 3 (J=0.24(1) cm{sup -1}). - Five two-dimensional divalent cobalt coordination polymers containing 4,4'-bipyridine (bpy) and substituted or unsubstituted glutarate ligands have been prepared and structurally characterized by single-crystal X-ray diffraction. Three contain dimeric {l_brace}Co{sub 2}(CO{sub 2}){sub 2}{r_brace} units, while two

  18. Heterobimetallic MOFs containing tetrathiocyanometallate building blocks: pressure-induced spin crossover in the porous {Fe(II)(pz)[Pd(II)(SCN)4]} 3D coordination polymer.

    PubMed

    Muñoz-Lara, Francisco J; Arcís-Castillo, Zulema; Muñoz, M Carmen; Rodríguez-Velamazán, J Alberto; Gaspar, Ana B; Real, José A

    2012-10-15

    Here we describe the synthesis, structure, and magnetic properties of two related coordination polymers made up of self-assembling Fe(II) ions, pyrazine (pz), and the tetrathiocyanopalladate anion. Compound {Fe(MeOH)(2)[Pd(SCN)(4)]}·pz (1a) is a two-dimensional coordination polymer where the Fe(II) ions are equatorially coordinated by the nitrogen atoms of four [Pd(SCN)(4)](2-) anions, each of which connects four Fe(II) ions, forming corrugated layers {Fe[Pd(SCN)(4)]}(∞). The coordination sphere of Fe(II) is completed by the oxygen atoms of two CH(3)OH molecules. The layers stack one on top of each other in such a way that the included pz molecule establishes strong hydrogen bonds with the coordinated methanol molecules of adjacent layers. Compound {Fe(pz)[Pd(SCN)(4)]} (2) is a three-dimensional porous coordination polymer formed by flat {Fe[Pd(SCN)(4)]}(∞) layers pillared by the pz ligand. Thermal analysis of 1a shows a clear desorption of the two coordinated CH(3)OH molecules giving a rather stable phase (1b), which presumably is a polymorphic form of 2. The magnetic properties of the three derivatives are typical of the high-spin Fe(II) compounds. However, compounds 1b and 2, with coordination sphere [FeN(6)], show thermal spin crossover behavior at pressures higher than ambient pressure (10(5) MPa).

  19. Dextran and polymer polyethylene glycol (PEG) coating reduce both 5 and 30 nm iron oxide nanoparticle cytotoxicity in 2D and 3D cell culture.

    PubMed

    Yu, Miao; Huang, Shaohui; Yu, Kevin Jun; Clyne, Alisa Morss

    2012-01-01

    Superparamagnetic iron oxide nanoparticles are widely used in biomedical applications, yet questions remain regarding the effect of nanoparticle size and coating on nanoparticle cytotoxicity. In this study, porcine aortic endothelial cells were exposed to 5 and 30 nm diameter iron oxide nanoparticles coated with either the polysaccharide, dextran, or the polymer polyethylene glycol (PEG). Nanoparticle uptake, cytotoxicity, reactive oxygen species (ROS) formation, and cell morphology changes were measured. Endothelial cells took up nanoparticles of all sizes and coatings in a dose dependent manner, and intracellular nanoparticles remained clustered in cytoplasmic vacuoles. Bare nanoparticles in both sizes induced a more than 6 fold increase in cell death at the highest concentration (0.5 mg/mL) and led to significant cell elongation, whereas cell viability and morphology remained constant with coated nanoparticles. While bare 30 nm nanoparticles induced significant ROS formation, neither 5 nm nanoparticles (bare or coated) nor 30 nm coated nanoparticles changed ROS levels. Furthermore, nanoparticles were more toxic at lower concentrations when cells were cultured within 3D gels. These results indicate that both dextran and PEG coatings reduce nanoparticle cytotoxicity, however different mechanisms may be important for different size nanoparticles.

  20. pH-value-controlled assembly of photoluminescent zinc coordination polymers in the mixed-ligand system

    NASA Astrophysics Data System (ADS)

    Liu, Kang; Hu, Hanbin; Sun, Jing; Zhang, Yiheng; Han, Jishu; Wang, Lei

    2017-04-01

    Three novel coordination polymers, [Zn(sdi)2(NO3)(H2O)]·NO3 (1), [Zn(sdi)2(H2O)2]·2NO3 (2) and [Zn(sdi)0.5(H2C3O4)(H2O)] (3), (sdi = N,N‧-sulfuryldiimidazole) have been synthesized and characterized by elemental analysis, IR spectroscopy, single crystal X-ray diffraction, powder X-ray diffraction and thermogravimetric analyses. These compounds have abundant structural chemistry ranging from zero-dimensional (0D) (1), one-dimensional (1D) (2), to three-dimensional (3D) (3) networks. Compound 1 displays a 0D structure which formed by [Zn(sdi)2]2 dimers. Compound 2 possesses 1D chain with closed loops. Notably, compound 3 exhibits a 3D (3,4)-connected net with a (63)(65·8) topology. Interestingly, compounds 1-3 were obtained under similar reaction conditions and the structural diversity of these coordination polymers illustrate the remarkable effect of pH on the self-assembling process. Moreover, the fluorescent properties of these compounds have been investigated.

  1. A luminescent lanthanide coordination polymer based on energy transfer from metal to metal for hydrogen peroxide detection.

    PubMed

    Zeng, Hui-Hui; Zhang, Li; Rong, Lian-Qing; Liang, Ru-Ping; Qiu, Jian-Ding

    2017-03-15

    A bimetal lanthanide coordination polymer nanoparticle (ATP-Ce/Tb-Tris CPNs) with good biocompatibility was synthesized in Tris-HCl buffer using adenosine triphosphate (ATP) molecules as the bridge ligands. The large absorption cross section and suitable emission energy of Ce(3+) matching to the adsorption energy of Tb(3+)((4)fn) results in the efficient energy transfer from Ce(3+) to Tb(3+), thus the synthesized ATP-Ce/Tb-Tris CPNs exhibit the characteristic green emission of Tb(3+). Such energy transfer from metal to metal in fluorescent lanthanide coordination polymer nanoparticles (Ln-CPNs) has been demonstrated. It is found that the oxidation of Ce(3+) in ATP-Ce/Tb-Tris CNPs to Ce(4+) would interrupt the energy transfer from Ce(3+) to Tb(3+), leading to fluorescence quenching of Tb(3+). On the basis of this quenching mechanism, ATP-Ce/Tb-Tris CPNs has been successfully used to detect reactive oxygen H2O2 with detection limit as low as 2nM. If glucose oxidase is present in the system, glucose can be determined using the ATP-Ce/Tb-Tris CNPs nanosensor.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Linking of trinuclear pivalate Fe2NiO(Piv)6 (Piv=O2CC(CH3)3) by 2,6-bis(4-pyridyl)-4-(1-naphthyl)pyridine (L) resulted in formation of 1D-porous coordination polymer Fe2NiO(Piv)6(L)·Solv, which was characterized in two forms: DMSO solvate Fe2NiO(Piv)6(L)(DMSO)·2.5DMSO (1) or water solvate Fe2NiO(Piv)6(L)(H2O) (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 Fe2NiO(Piv)6(L) was confirmed by the measurements of N2 and H2 adsorption at 77 K. Potential barriers of the different molecules diffusion through pores were estimated by the means of molecular mechanics.

  3. A mixed-ligand approach for spin-crossover modulation in a linear Fe(II) coordination polymer.

    PubMed

    Calvo Galve, Néstor; Coronado, Eugenio; Giménez-Marqués, Mónica; Mínguez Espallargas, Guillermo

    2014-05-05

    In this work, we present a family of Fe(II) coordination polymers of general formula [Fe(btzx)(3-3x)(btix)(3x)](ClO4)2 with interesting spin-crossover properties. These coordination polymers have been synthesized using chemical mixtures of two different but closely related ligands, 1,4-bis(tetrazol-1-ylmethyl)benzene (btzx) and 1,4-bis(triazol-1-ylmethyl)benzene (btix), and the effect of a gradual substitution of the ligand in the spin transition temperature has been investigated. Several chemical mixtures have been structurally characterized by X-ray powder diffraction indicating a clear critical amount in the composition of the mixture after which mixed phases rather than a single phase comprising mixed components are observed. Importantly, this approach causes the appearance of a new transition at lower temperatures that is not present in the pure [Fe(L)3](ClO4)2 systems.

  4. Syntheses, structures, electrochemistry and catalytic oxidation degradation of organic dyes of two new coordination polymers derived from Cu(II) and Mn(II) and 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene

    NASA Astrophysics Data System (ADS)

    Song, Ming; Mu, Bao; Huang, Ru-Dan

    2017-02-01

    Two new coordination polymers (CPs), namely, [Cu2(ttbz)(H2btc)2(OH)]n (1) and [Mn(ttbz)2(H2O)2]n (2) (Httbz =1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene, H3btc =1,3,5-benzenetricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a (3,5,5,5)-connected 2D layer with a Schläfli symbol of {3·42}{3·440.520.63}{320.440.520.62}{320.440.530.6}, in which the ttbz- ligand can be described as μ5-bridge, linking Cu(II) ions into a 2D layer and H2btc- ions play a supporting role in complex 1. The ttbz- ligand in complex 2 represents the bridging coordination mode, connecting two Mn(II) ions to form the infinite 1D zigzag chains, respectively, which are further connected by two different types of hydrogen bonds to form a 3D supramolecular. Furthermore, catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated at room temperature in aqueous solutions, indicating these complexes may be applicable to color removal in a textile wastewater stream and practical applications in areas of electrocatalytic reduction toward nitrite, respectively.

  5. Dicarboxylate-controlled three Zn(II) coordination polymers incorporating flexible 1,2-bis(imidazol-1‧-yl)ethane ligand: Syntheses, structures, thermal stabilities and photoluminescent properties

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

    Three mixed-ligand Zn(II) coordination polymers (CPs) of the formula {[Zn2(bime)2(adip)2]ṡ(H2O)5}n (1), {[Zn(bime)(ipa)]ṡ(H2O)3}n (2), {[Zn(bime)(tpa)]ṡ(H2O)ṡ(CH3OH)}n (3) (bime = 1,2-bis(imidazol-1'-yl)ethane, H2adip = adipic acid, H2ipa = isophthalic acid and H2tpa = terephthalic acid) were synthesized. All CPs have been characterized by element analysis, powder X-ray diffraction (PXRD), IR and X-ray single-crystal diffraction. Complexes 1 and 2 exhibit similar wavy two-dimensional (2D) sheets with 44-sql topology. Compared to 1, complex 2 contains a larger window owing to the different conformation of bime ligand. In both 1 and 2, we observed 1D water chain filling in the 44-sql net. In 3, the bime acts as a bidentate ligand and the tpa adopts a μ2-η1,η1 coordinated mode which links the Zn(II) ions to form a 2D 63-hcb net. The results suggest that the dicarboxylates play crucial roles in the formation of the different structures. In addition, the thermal stabilities and the photoluminescence properties of them were also investigated.

  6. Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal

    SciTech Connect

    Llano-Tomé, Francisco; Bazán, Begoña; Urtiaga, Miren-Karmele; Barandika, Gotzone; Antonia Señarís-Rodríguez, M.; and others

    2015-10-15

    Combination of polycarboxylate anions and dipyridyl ligands is an effective strategy to produce solid coordination frameworks (SCF) which are crystalline materials based on connections between metal ions through organic ligands. In this context, this work is focused on two novel Cu{sup II}-based SCFs exhibiting PDC (2,5-pyridinedicarboxylate) and bpa (1,2-di(4-pyridyl)ethane), being the first structures reported in literature containing both ligands. Chemical formula are [Cu{sub 2}[(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·3H{sub 2}O·DMF (1), and [Cu{sub 2}(PDC){sub 2}(bpa)(H{sub 2}O){sub 2}]·7H{sub 2}O (2), where DMF is dimethylformamide. Compounds 1 and 2 have been characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric (TG) analysis, differential thermal analysis (DTA) and dielectric measurements. The crystallographic analysis revealed that compounds 1 and 2 can be described as herringbone-type layers formed by helicoidal Cu-PDC-Cu chains connected through bpa ligands. Solvent molecules are crystallized between the layers, providing the inter-layer connections through hydrogen bonds. Differences between both compounds are attributable to the flexibility of bpa (in 2D) as well as to the 3D packing of the layers which is solvent dependent. This fact results in the fact that compound 2 is the most regular 3-c herringbone array reported so far. The structural dynamism of these networks is responsible for the crystalline to-amorphous to-crystalline (CAC) transformation from compound 1 to compound 2. Crystallochemical features for both compounds have also been studied and compared to similar 3-connected herringbone-arrays. - Graphical abstract: Cu-PDC-bpa 3-c herringbone arrays. - Highlights: • The most ideal herringbone array reported so far is a Cu-PDC-bpa SCF. • Conformational freedom of bpa results in 2D and 3D flexibility of the SCFs. • The flexibility of the SCFs is related to a phase transformation. • Dielectric

  7. A new one-dimensional NiII coordination polymer with a two-dimensional supra­molecular architecture

    PubMed Central

    Zhong, Kai-Long

    2017-01-01

    A new one-dimensional NiII coordination polymer of 1,3,5-tris­(imidazol-1-ylmeth­yl)benzene, namely catena-poly[[aqua­(sulfato-κO)hemi(μ-ethane-1,2-diol-κ2 O:O′)[μ3-1,3,5-tris­(1H-imidazol-1-ylmeth­yl)benzene-κ3 N 3,N 3′,N 3′′]nickel(II)] ethane-1,2-diol monosolvate monohydrate], {[Ni(SO4)(C18H18N6)(C2H6O2)0.5(H2O)]·C2H6O2·H2O}n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. The NiII cation is coordinated by three N atoms of three different 1,3,5-tris­(imidazol-1-ylmeth­yl)benzene ligands, one O atom of an ethane-1,2-diol mol­ecule, by a sulfate anion and a water mol­ecule, forming a distorted octa­hedral NiN3O3 coordination geometry. The tripodal 1,3,5-tris­(imidazol-1-ylmeth­yl)benzene ligands link the NiII cations, generating metal–organic chains running along the [100] direction. Adjacent chains are further connected by O—H⋯O hydrogen bonds, resulting in a two-dimensional supermolecular architecture running parallel to the (001) plane. Another water mol­ecule and a second ethane-1,2-diol mol­ecule are non-coordinating and are linked to the coordinating sulfate ions via O—H⋯O hydrogen bonds. PMID:28217340

  8. Electrical conductivity and luminescence in coordination polymers based on copper(I)-halides and sulfur-pyrimidine ligands.

    PubMed

    Gallego, Almudena; Castillo, Oscar; Gómez-García, Carlos J; Zamora, Félix; Delgado, Salome

    2012-01-02

    The solvothermal reactions between pyrimidinedisulfide (pym(2)S(2)) and CuI or CuBr(2) in CH(2)Cl(2):CH(3)CN lead to the formation of [Cu(11)I(7)(pymS)(4)](n) (pymSH = pyrimidine-2(1H)-thione) (1) and the dimer [Cu(II)(μ-Br)(Br)L](2) (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde) (2). In the later reaction, there is an in situ S-S, S-C(sp(2)), and C(sp(2))-N multiple bond cleavage of the pyrimidinedisulfide resulting in the formation of 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde. Interestingly, similar reactions carried out just with a change in the solvent (H(2)O:CH(3)CN instead of CH(2)Cl(2):CH(3)CN) give rise to the formation of coordination polymers with rather different architectures. Thus, the reaction between pym(2)S(2) and CuI leads to the formation of [Cu(3)I(pymS)(2)](n) (3) and [CuI(pym(2)S(3))] (pym(2)S(3) = pyrimidiltrisulfide) (4), while [Cu(3)Br(pymS)(2)](n) (5) is isolated in the reaction with CuBr(2). Finally, the solvothermal reactions between CuI and pyrimidine-2-thione (pymSH) in CH(2)Cl(2):CH(3)CN at different ratios, 1:1 or 2:1, give the polymers [Cu(2)I(2)(pymSH)(2)](n) (6) and [Cu(2)I(2)(pymSH)](n) (7), respectively. The structure of the new compounds has been determined by X-ray diffraction. The studies of the physical properties of the novel coordination polymers reveal that compounds 3 and 5 present excellent electrical conductivity values at room temperature, while compounds 1, 3, and 5-7 show luminescent strong red emission at room temperature.

  9. 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.

  10. 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

  11. Coordination-directed one-dimensional coordination polymers generated from a new oxadiazole bridging ligand and HgX2 (X=Cl, Br and I).

    PubMed

    Yang, Rui; Ma, Jian Ping; Huang, Ru Qi; Dong, Yu Bin

    2011-06-01

    A new 1,3,4-oxadiazole bridging bent organic ligand, 2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole, C(28)H(24)N(4)O(3), L, has been used to create three novel one-dimensional isomorphic coordination polymers, viz. catena-poly[[[dichloridomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgCl(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n), catena-poly[[[dibromidomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgBr(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n), and catena-poly[[[diiodidomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgI(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n). The free L ligand itself adopts a cis conformation, with the two terminal pyridine rings and the central oxadiazole ring almost coplanar [dihedral angles = 5.994 (7) and 9.560 (6)°]. In the Hg(II) complexes, however, one of the flexible pyridylmethyl arms of ligand L is markedly bent and helical chains are obtained. The Hg(II) atom lies in a distorted tetrahedral geometry defined by two pyridine N-atom donors from two L ligands and two halide ligands. The helical chains stack together via interchain π-π interactions that expand the dimensionality of the structure from one to two. The methanol solvent molecules link to the complex polymers through O-H···N and O-H···O hydrogen bonds.

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

    SciTech Connect

    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.

  13. Ferromagnetic interactions through triple hydrogen bonds in the coordination polymers of alpha,alpha'-dihydroxy-bibenzyl-4,4'-dicarboxylate.

    PubMed

    Ma, Yu; Cheng, Ai-Ling; Gao, En-Qing

    2010-04-14

    Three transition metal coordination polymers with alpha,alpha'-dihydroxy-bibenzyl-4,4'-dicarboxylate (L) were synthesized, and structurally and magnetically characterized. The three compounds, formulated as [M(L)(H(2)O)(4)].2H(2)O (M = Co(ii), Mn(ii) and Ni(ii)), are isomorphic and consist of one-dimensional coordination chains formed by the dicarboxylate ligand bridging the metal ions using monodentate carboxylate groups. Intriguingly, the [M(COO)(2)(H(2)O)(4)] spheres from different coordination chains are linked through triple O-H...O bridges to give the rare hydrogen bonded chains with [M(O-H...O)(3)M] helicate motifs, which represent good systems suitable for investigating the exchange coupling through hydrogen bonding. Magnetic studies on Ni(ii) and Co(ii) compounds reveal that the triple hydrogen bonding bridge transmits ferromagnetic coupling, with J = 3.46 cm(-1) for the Ni(ii) compound and J = 1.12 cm(-1) for the Co(ii) compound.

  14. Photoisomerization of a maleonitrile-type salen Schiff base and its application in fine-tuning infinite coordination polymers.

    PubMed

    Lin, Chun-Wei; Chou, Pi-Tai; Liao, Yong-Hong; Lin, Ying-Chih; Chen, Ching-Ting; Chen, Yu-Chun; Lai, Chin-Hung; Chen, Bo-So; Liu, Yi-Hung; Wang, Chih-Chieh; Ho, Mei-Lin

    2010-03-22

    Strategically designed salen ligand 2,3-bis[4-(di-p-tolylamino)-2-hydroxybenzylideneamino]maleonitrile (1), which has pronounced excited-state charge-transfer properties, shows a previously unrecognized form of photoisomerization. On electronic excitation (denoted by an asterisk), 1Z*-->1E isomerization takes place by rotation about the C2--C3 bond, which takes on single-bond character due to the charge-transfer reaction. The isomerization takes place nonadiabatically from the excited-state (1Z) to the ground-state (1E) potential-energy surface in the singlet manifold; 1Z and 1E are neither thermally inconvertible at ambient temperature (25-30 degrees C), nor does photoinduced reverse 1E*-->1Z (or 1Z*) isomerization occur. Isomers 1Z and 1E show very different coordination chemistry towards a Zn(II) precursor. More prominent coordination chemistry is evidenced by a derivative of 1 bearing a carboxyl group, namely, N,N'-dicyanoethenebis(salicylideneimine)dicarboxylic acid (2). Applying 2Z and its photoinduced isomer 2E as building blocks, we then demonstrate remarkable differences in morphology (sphere- and needlelike nanostructure, respectively) of their infinite coordination polymers with Zn(II).

  15. Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

    PubMed

    Zhu, Zhengguang; Xu, Na; Yu, Qiuping; Guo, Lei; Cao, Hui; Lu, Xinhua; Cai, Yuanli

    2015-08-01

    Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts.

  16. Structural and magnetic properties of layered copper(II) coordination polymers intercalating s and f metal ions.

    PubMed

    Navarro, Jorge A R; Barea, Elisa; Salas, Juan M; Masciocchi, Norberto; Galli, Simona; Sironi, Angelo

    2007-04-16

    The nanoporous coordination polymer [Cu(pyrimidin-2-olate-N1,N3)2]n (1C) of the sodalite zeotype sorbs a variety of metal nitrates [M(NO3)m, M = Na+, K+, Rb+, Tl+, Ca2+, Sr2+, Ba2+, Pb2+, La3+, Nd3+, Gd3+, Er3+] from H2O/MeOH solutions, with a concomitant structural change to a layered [Cu(pyrimidin-2-olate-N1,N3)2]n.[M(NO3)m]n/2 (MNO3@1L) coordination framework. Single-crystal X-ray diffraction analyses revealed that the layers are based on Cu4(pyrimidin-2-olate-N1,N3)4 square grids of copper(II) ions bridged by N1,N3 exobidentate ligands, displaying a structural motif of the metallacalix[4]arene type in pinched cone conformation. The interlayer space is occupied by the guest metal nitrates, each metal being coordinated by (at least) the four oxygen atoms of a metallacalix[4]arene. Magnetic measurements on the MNO3@1L series denoted a weak ferromagnetic ordering taking place below the Néel temperatures (typically close to 35 K), arising from spin-canting phenomena of the antiferromagnetically coupled copper centers. When M = Nd3+, Gd3+, or Er3+, additional magnetic ordering is observed at lower temperatures, which, on the basis of static and dynamic magnetic susceptibility measurements, can be attributed to copper- lanthanide interactions.

  17. Synthesis, structures and photocatalytic properties of two new Co(II) coordination polymers based on 5-(benzyloxy)isophthalate ligand

    NASA Astrophysics Data System (ADS)

    Li, Xia; Li, Jing; Li, Ming-Kai; Fei, Zhou

    2014-02-01

    Two new Co(II) coordination polymer, namely [Co2(L)2(H2O)]n (1) and [Co(L)(phen)(H2O)]n·xH2O (2) (H2L = 5-(benzyloxy)isophthalic acid, phen = 1,10-phenanthroline) have been hydrothermally synthesized and characterized by elemental analysis, powder X-ray diffraction, thermal analysis and single crystal X-ray analysis. The molecular structure of 1 contains two Co(II) ions, two L2- ligands and one coordinated water molecule, which further extends into a complicated 3D framework with the tails of L2- ligands filling in the hexagonal channels, and the molecular structure of 2 contains one Co(II) ions, one L2- ligands, one phen ligands, one coordinated water molecule and half of the water molecule of crystallization, which further extends into a 1D chain structure. In addition, photocatalytic investigation on compounds 1 and 2 reveals that they are active catalyst for degradation of methyl blue.

  18. Mixed ligand coordination polymers with flexible bis-imidazole linker and angular sulfonyldibenzoate: Crystal structure, photoluminescence and photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Bisht, Kamal Kumar; Rachuri, Yadagiri; Parmar, Bhavesh; Suresh, Eringathodi

    2014-05-01

    Four ternary coordination polymers (CPs) namely, {[Ni(SDB)(BITMB)(H2O)]·H2O}n (CP1), {[Cd(SDB)(BITMB) (H2O)]·(THF)(H2O)}n (CP2), {[Zn2(SDB)2(BITMB)]·(THF)2}n (CP3) and {[Co2(SDB)2(BITMB)]·(Dioxane)3}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.

  19. 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

    2013-10-07

    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.

  20. 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

  1. Cu-PDC-bpa solid coordination frameworks (PDC=2,5-pyrindinedicarboxylate; bpa=1,2-DI(4-pyridil)ethane)): 2D and 3D structural flexibility producing a 3-c herringbone array next to ideal

    NASA Astrophysics Data System (ADS)

    Llano-Tomé, Francisco; Bazán, Begoña; Urtiaga, Miren-Karmele; Barandika, Gotzone; Antonia Señarís-Rodríguez, M.; Sánchez-Andújar, Manuel; Arriortua, María-Isabel

    2015-10-01

    Combination of polycarboxylate anions and dipyridyl ligands is an effective strategy to produce solid coordination frameworks (SCF) which are crystalline materials based on connections between metal ions through organic ligands. In this context, this work is focused on two novel CuII-based SCFs exhibiting PDC (2,5-pyridinedicarboxylate) and bpa (1,2-di(4-pyridyl)ethane), being the first structures reported in literature containing both ligands. Chemical formula are [Cu2[(PDC)2(bpa)(H2O)2]·3H2O·DMF (1), and [Cu2(PDC)2(bpa)(H2O)2]·7H2O (2), where DMF is dimethylformamide. Compounds 1 and 2 have been characterized by means of X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric (TG) analysis, differential thermal analysis (DTA) and dielectric measurements. The crystallographic analysis revealed that compounds 1 and 2 can be described as herringbone-type layers formed by helicoidal Cu-PDC-Cu chains connected through bpa ligands. Solvent molecules are crystallized between the layers, providing the inter-layer connections through hydrogen bonds. Differences between both compounds are attributable to the flexibility of bpa (in 2D) as well as to the 3D packing of the layers which is solvent dependent. This fact results in the fact that compound 2 is the most regular 3-c herringbone array reported so far. The structural dynamism of these networks is responsible for the crystalline to-amorphous to-crystalline (CAC) transformation from compound 1 to compound 2. Crystallochemical features for both compounds have also been studied and compared to similar 3-connected herringbone-arrays.

  2. Luminescent zinc and cadmium complexes incorporating 1,3,5-benzenetricarboxylate and a protonated kinked organodiimine: From a hydrogen-bonded layer motif to thermally robust two-dimensional coordination polymers

    SciTech Connect

    Braverman, Maxwell A.; Supkowski, Ronald M.; LaDuca, Robert L.

    2007-06-15

    Hydrothermal treatment of zinc chloride, 1,3,5-benzenetricarboxylic acid (H{sub 3}BTC), and 4,4'-dipyridylamine (dpa) afforded two different complexes depending on reaction conditions, which were characterized by single-crystal X-ray diffraction, infrared spectroscopy, and elemental analysis. Under acidic conditions, a discrete neutral molecular species with formulation [Zn(HBTC){sub 2}(Hdpa){sub 2}] (1) was isolated, which aggregates into two-dimensional hydrogen-bonded layers. Under more basic conditions, the two-dimensional layered coordination polymer [Zn(BTC)(Hdpa)] (2) is obtained, which manifests covalent linkage of [Zn(BTC)(Hdpa)] serpentine chain motifs into 3-connected undulating 4.8{sup 2} topology 2-D layers. Both 1 and 2 possess tetrahedral coordination at Zn. Use of cadmium nitrate in the synthesis resulted in [Cd(BTC)(H{sub 2}O)(Hdpa)] (3), which displays a similar layer topology as 2 but with significant adjustments imparted by octahedral coordination at Cd. In all cases, supramolecular hydrogen bonding promoted by Hdpa ligands provide an important assistive structure-directing role. All materials display blue luminescence upon excitation with ultraviolet light, ascribed to intraligand transitions. Crystallographic data: 1: monoclinic, C2/c, a=25.389(6) A, b=9.811(2) A, c=17.309(4) A, and {beta}=128.957(3){sup o}, 2: monoclinic, P2{sub 1}/c, a=13.212(17)c, b=17.15(2) A, c=7.506(10) A, and {beta}=93.71(2){sup o}, and 3: monoclinic, C2/c, a=14.241(6) A, b=15.218(6) A, c=17.976(7) A, and {beta}=109.330(6){sup o}. - Graphical abstract: Hydrothermal synthesis has afforded a family of luminescent complexes based on divalent d {sup 10} cations with 1,3,5-benzenetricarboxylate (BTC) and 4,4'-dipyridylamine (dpa) ligands. [Zn(HBTC){sub 2}(Hdpa){sub 2}] (1) is a discrete neutral molecular species. [Zn(BTC)(Hdpa)] (2, pictured) and [Cd(BTC)(H{sub 2}O)(Hdpa)] (3) are 2-D coordination polymers with different morphologies depending on coordination geometry at the

  3. 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

  4. 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.

  5. Synthesis and structure of a stable pentavalent-uranyl coordination polymer.

    PubMed

    Natrajan, Louise; Burdet, Fabien; Pécaut, Jacques; Mazzanti, Marinella

    2006-06-07

    The polymeric complex {[UO2Py5][KI2Py2]}n was isolated by controlled oxidation of uranium tris-iodide in pyridine and structurally characterized using X-ray diffraction. The described synthetic method allows us to isolate a stable derivative of the elusive pentavalent UO2+ species providing a potential starting material for the development of anhydrous UO2+ coordination chemistry.

  6. 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.

  7. Anion effect on the topological frameworks of a series of manganese coordination polymers based on 1,4-bis(imidazol-1-yl)-benzene: Syntheses, crystal structures and magnetic properties

    SciTech Connect

    Ye, Gan; Zou, Kang-Yu; Yang, Ying; Wang, Jun-Jie; Gou, Xiao-Feng; Li, Zuo-Xi

    2015-05-15

    In this work, the rod-like ligand 1,4-bis(imidazol-1-yl)-benzene (bib) has been utilized as a building block to perform counterion researches on the structural diversities of coordination polymers. A series of new manganese compounds, ([Mn(bib){sub 3}(ClO{sub 4}){sub 2}](CHCl{sub 3}){sub 2}){sub n} (1), [Mn(bib){sub 2}(N{sub 3}){sub 2}]{sub n} (2), [Mn(bib){sub 2}(HCO{sub 2}){sub 2}]{sub n} (3), [Mn(bib){sub 2}(Ac){sub 2}]{sub n} (4), ([Mn(bib){sub 2}(CF{sub 3}SO{sub 3}){sub 2}](CH{sub 2}Cl{sub 2}){sub 4}){sub n} (5), and [Mn(bib){sub 2}(SO{sub 4})]{sub n} (6) have been successfully synthesized. Compound 1 shows a 3D interpenetrating α-Po network only based on the bib linker. Compounds 2 and 3 exhibit a 2D (4,4) layer with parallel and incline interpenetration, respectively. Compounds 4 and 5 display a parallel-packing 2D (4,4) layer with the porosity of 23.4% and 61.4%, respectively. Compound 6 furnishes a 3D α-Po framework with a 2D (4,4) layer pillared by the μ{sub 2}-SO{sub 4}{sup 2−} ion. The structural diversities among 1–6 have been carefully discussed, and the roles of counterions (from coordination affinity and molecular size) in the self-assembly of coordination polymers have also been well documented. Furthermore, magnetic properties of 6 have been carefully studied. - Graphical abstract: Six new compounds have been successfully synthesized. Structural studies reveal that the topology, entanglement and porosity are tunable by the counterion. Furthermore, the weak ferromagnetic coupling is conducted in 6. - Highlights: • Six new Mn{sup II} compounds have been synthesized. • Compounds 1–3 exhibit diverse interpenetrating frameworks. • Compounds 4 and 5 exhibit 3D packing porous architectures. • The tunable effect of counterion has been documented. • Magnetic properties of 6 have been studied by fitting the data.

  8. Aromatic N-oxides in construction of different carboxylate coordination polymers of zinc(II), cadmium(II) and mercury(II)

    NASA Astrophysics Data System (ADS)

    Sarma, Rupam; Baruah, Jubaraj B.

    2011-09-01

    The coordination polymers [Zn(C 6H 5COO) 2(PNO)] n ( 1), [Zn 2(C 6H 5COO) 4(4,4'-BPNO)] n ( 2), [Zn 4(C 6H 4C 2O 4) 4(4,4'-BPNO) 2(H 2O) 5] n· nH 2O ( 3), [Cd(C 6H 5COO) 2(PNO)] n ( 4), [Cd 3(C 6H 5COO) 6(4,4'-BPNO) 2] n·2 nH 2O ( 5), [Cd(C 6H 4C 2O 4)(4,4'-BPNO)(H 2O)] n ( 6) and [Hg(C 6H 5COO) 2(4,4'-BPNO) 2] n ( 7), (where PNO = pyridine N-oxide, 4,4'-BPNO = 4,4'-bipyridyl- N,N'-dioxide) are synthesized and structurally characterized. The structures of these coordination polymers exhibit mononuclear to trinuclear nodes built by ligation of carboxylate to metal ions connected by N-oxide ligands. Pyridine N-oxide interconnects metal nodes by acting as μ 2-bridging ligand in complexes 1, and 4. In the linear coordination polymer 2, the paddle wheel structure of zinc(II) benzoate units are interconnected by 4,4'-bipyridyl- N,N'-dioxide which acts as a bidentate spacer ligand adopting a trans μ 2-η 1 : η 1 coordination mode. The polymeric structure of 3 formed by terephthalate and 4,4'-bipyridyl- N,N'-dioxide with zinc(II) contains self-assembled dinuclear Zn 2O 2 type of carboxylate cores, with 4,4'-bipyridyl- N,N'-dioxide coordinating through cis μ 2-η 1 : η 1 coordination mode. The cadmium coordination polymer 5, comprising of 4,4'-bipyridyl- N,N'-dioxide and benzoate, has trinuclear cadmium benzoate cores wherein the terminal cadmium ions are interconnected by monodentate 4,4'-bipyridyl- N,N'-dioxide bridges. The coordination polymer 6 comprises of mononuclear cadmium nodes independently bridged by terephthalate and 4,4'-bipyridyl- N,N'-dioxide thereby leading to a 3-fold interpenetrated three dimensional network. Double helical polymeric structure is observed in the coordination polymer 7 derived from mononuclear mercury(II) benzoate nodes bridged by 4,4'-bipyridyl- N,N'-dioxide with cis μ 2-η 1 : η 1 coordination mode.

  9. Cd(II)-coordination polymers based on tetracarboxylic acid and diverse bis(imidazole) ligands: Synthesis, structural diversity and photoluminescence properties

    NASA Astrophysics Data System (ADS)

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Taş, Murat

    2017-01-01

    Three new Cd(II)-coordination polymers, namely, {[Cd2(μ6-ao2btc)(μ-1,5-bipe)2]·2H2O}n (1), {[Cd2(μ6-ao2btc)(μ-1,4-bix)2]n·2DMF} (2) and {[Cd2(μ8-abtc)(μ-1,4-betix)]·DMF·H2O}n (3) (ao2btc=di-oxygenated form of 3,3‧,5,5‧-azobenzenetetracarboxylate, 1,5-bipe: 1,5-bis(imidazol-1yl)pentane, 1,4-bix=1,4-bis(imidazol-1ylmethyl)benzene, 1,4-betix=1,4-bis(2-ethylimidazol-1ylmethyl)benzene) were synthesized with 3,3‧,5,5‧-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1-3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the rare sqc27 topology. When semi-flexible substituted bis(imidazole) linker was used, 3D framework of complex 3 was obtained with the paddlewheel Cd2(CO2)4-type binuclear SBU. Moreover, thermal and photoluminescence properties of the complexes were determined in detailed.

  10. Syntheses, structures, and properties of transition metal coordination polymers based on a long semirigid tetracarboxylic acid and multidentate N-donor ligands

    NASA Astrophysics Data System (ADS)

    Gao, Peng; Bai, Hui; Bing, Ying-Ying; Hu, Ming

    2016-02-01

    Six transition metal coordination polymers based on a semirigid tetracarboxylic acid and the multidentate N-donor ligands have been synthesized by the hydrothermal method, namely, {[Co(H2obda) (μ2-H2O) (H2O)2]·2H2O}n (1), {[Co(obda)0.5(bpe) (H2O)2]·3H2O}n (2), {[Zn(H2obda) (H2O)4]·H4obda·6H2O}n (3), {[Zn(bpy) (H2O)4]·H2obda}n (4), {[Ni(bpy) (H2O)4]·H2obda}n (5) and {[Cu(H2obda) (bpy)2]}n (6) (H4obda = 1,4-bis(4-oxy-1,2-benzene dicarboxylic acid)benzene, bpe = 1,2-Bis(4-pyridyl)ethylene), bpy = 4,4‧-bipyridine). Compounds 1-6 were structurally characterized by the elemental analyses, infrared spectra, and single crystal X-ray diffractions. Compounds 1-2 exhibit the 2D quadrilateral and polygonal layered grid structures, respectively; a 3D supramolecular structure of 2 has been build via π···π and hydrogen bonds interactions. Compounds 3-6 reveal the 1D zigzag and linear chains structures, respectively; furthermore, 3-5 display the diverse 3D supramolecular structures via hydrogen bonds, respectively. The 1-D infinite water chain in 3 has been found between the lattice water molecules. In addition, the thermogravimetric analyses of 1-6, magnetic property of 1, and photoluminescence of 3-4 have been investigated, respectively.

  11. Three two-dimensional coordination polymers constructed from transition metals and 2,3-norbornanedicarboxylic acid: Hydrothermal synthesis, crystal structures and photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Zhang, Jia; Wang, Chong-Chen

    2017-02-01

    Three novel coordination polymers based on transition metals like Co(II), Cu(II) and Mn(II), namely [Co2(bpy)2(nbda)2(H2O)2]·2H2O (denoted as BUC-1), [Cu2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-2), [Mn2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-3), (where bpy = 4,4‧-bipyridine, H2nbda = 2,3-norbornanedicarboxylic acid, BUC = Beijing University of Civil Engineering and Architecture), were synthesized under hydrothermal conditions, and characterized by CNH elemental analyses (EA), Fourier Transform infrared spectroscopy (FTIR), and single crystal X-ray diffraction (SCXRD). BUC 1-3 were isostructural and crystallized in the monoclinic space group C2/c, in which the corresponding metal atoms were linked by typical bidentate bpy ligands into two adjacent 1D [M1(bpy)]n2n+ and [M2(bpy)]n2n+ (M = Co(II), Cu(II), Mn(II)), further joined by versatile nbda2- ligands into 2D [M2(bpy)2(nbda)2]n sheets. Finally, three-dimensional supramolecular frameworks were constructed with the aid of the intermolecular hydrogen bonding interactions. BUC 1-3 exhibited different photocatalytic degradation ability to decompose methylene blue (MB) and methyl orange (MO) under UV light irradiation. Additionally, a possible photocatalytic mechanism HOMO-LUMO was proposed and discussed, which was further confirmed by radicals trapping experiments using isopropanol as radical scavenger.

  12. Thermal, pressure and light induced spin transition in the two-dimensional coordination polymer [Fe(pmd)2[Cu(CN)2]2].

    PubMed

    Agustí, Gloria; Thompson, Amber L; Gaspar, Ana B; Muñoz, M Carmen; Goeta, Andrés E; Rodríguez-Velamazán, José Alberto; Castro, Miguel; Burriel, Ramón; Real, José Antonio

    2008-02-07

    A complete structural, calorimetric, and magnetic characterisation of the 2D coordination spin crossover polymer [Fe(pmd)(2)[Cu(CN)(2)](2)] is reported. The crystal structure has been investigated below room temperature at 180 K and 90 K, and at 30 K after irradiating the sample at low temperature with green light (lambda = 532 nm). The volume cell contraction through the thermal spin transition is only 18 A(3) which is lower than the usually observed value of around 25-30 A(3) while the average Fe-N bond distances decrease by the typical value of about 0.19 A. The structural data of the irradiated state indicate that the high spin state is well induced since the cell parameters are consistent with the data at 180 K. Calorimetric and photo-calorimetric experiments have also been performed. The entropy content for the thermal spin transition, DeltaS = 35-37 J mol(-1) K(-1) lies in the lowest range of the typical values and correlates with the low volume cell contraction. The combination of the crystallographic and calorimetric data predicts, in accordance with a mean-field approach, a linear pressure dependence of the critical temperature with a slope of 302 K GPa(-1). Magnetic measurements under pressure reveal an anomalous behaviour since the critical temperature and hysteresis do not change up to 0.22 GPa but an apparent linear dependence is obtained for higher pressures (up to 0.8 GPa) with a slope two times higher than the mean-field estimation.

  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. Hydrothermal synthesis, crystal structure and properties of a novel chain coordination polymer constructed by tetrafunctional phosphonate anions and cobalt ions

    SciTech Connect

    Guan, Lei; Wang, Ying

    2015-08-15

    A novel cobalt phosphonate, [Co(HL)(H{sub 2}O){sub 3}]{sub n} (1) (L=N(CH{sub 2}PO{sub 3}H){sub 3}{sup 3−}) has been synthesized by hydrothermal reaction at 150 °C and structurally characterized by X-ray diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Complex 1 features a 1D chain structure with double-channel built from CoO{sub 6} octahedra bridged together by the phosphonate groups. Each cobalt ion is octahedrally coordinated by three phosphonate oxygen atoms and three water molecules. The coordinated water molecules can form the hydrogen bonds with the phosphonate oxygen atoms to link the 1D chains, building a 2D layered structure, further resulting in a 3D network. The luminescence spectrum indicates an emission maximum at 435 nm. The magnetic susceptibility curve exhibits a dominant antiferromagnetic behavior with a weakly ferromagnetic component at low temperatures. - Graphical abstract: The connectivity between cobalt ions and the ligands results in a chain structure with a 1D double-channel structure, which is constructed by A-type subrings and B-type subrings. - Highlights: • The tetrafunctional phosphonate ligand was used as the ligand. • A novel chain structure can be formed by A-type rings and B-type rings. • Two types of rings can form a 1D double-channel structure, along the c-axis.

  16. Rapid microwave synthesis and photoluminescence properties of rare earth-based coordination polymer core-shell particles

    NASA Astrophysics Data System (ADS)

    Huang, Shuang; Xu, Hualan; Wang, Mengya; Zhong, Shengliang; Zeng, Chenghui

    2016-12-01

    Coordination polymer (CP) core-shell particles, with Eu-based CP as the core and La-based CP as the shell, were prepared using a facile microwave heating method. Pyridine-2, 5-dicarboxylic acid (PDA) was selected as the organic building blo, and DMF was used as the solvent. SEM and TEM images show that the resultant cores are nanospheres with diameters of 200-400 nm. Products with different shell thickness were prepared. The luminescence properties of the core-shell structures were studied and the influence of the La-based CP shell on the photoluminescence properties of the core were investigated. The fluorescence intensity and lifetime of the Eu-based CP core were varied with the addition of shell thickness. Both of them increases at first and then decreases with the increase of shell thickness.

  17. Tunable white-light emission PMMA-supported film materials containing lanthanide coordination polymers: preparation, characterization, and properties.

    PubMed

    Chen, Wei; Fan, Ruiqing; Zhang, Huijie; Dong, Yuwei; Wang, Ping; Yang, Yulin

    2017-03-27

    A series of lanthanide coordination polymers(LnCPs) containing both light and heavy rare-earth elements, namely {[Eu2(pydc)3(H2O)]·2H2O}n (1-Eu, H2pydc = pyridine-2,3-dicarboxylic acid), [Ln(pyc)2(Hpyc)(NO3)]n (Ln = Nd (2-Nd), Sm (3-Sm), Eu (4-Eu), Gd (5-Gd), Tb (6-Tb), Ho (7-Ho), and Er (8-Er), Hpyc = pyridine-3-carboxylic acid), has been synthesized under hydro(solvo)thermal conditions and fully characterized. The crystal structure analysis indicates that in situ decarboxylation of H2pydc occurred in the synthesis process of 2-Nd-8-Er. Coordination polymer 1-Eu displays a 3-D pcu network with central-symmetric quad-core structural units [Eu4(COO)6] linked by 1-D chains. 2-Nd-8-Er are of triple helical chain enantiomeric pair 61/65 axis, and can be further linked through two separate kinds of Hbonding interaction to form a mirror symmetrical 3-D framework; the final topological symbol of the jointly connected network is rare {4(7)·6(8)}. Solid-state luminescence studies show that the emission spectra of these LnCPs cover both the visible and near-infrared luminescence region. 2-Nd exhibits characteristic (4)F3/2 → (4)IJ/2 (J = 9, 11, 13) transition NIR emission. 1-Eu and 4-Eu provide characteristic (5)D0 → (7)FJ intense and bright red luminescence, while 4-Eu exhibits better luminescence performance because of the presence of the O-H oscillators within 1-Eu. 6-Tb exhibits characteristic (5)D4 → (7)FJ intense and bright green luminescence. Furthermore, through doping with PMMA polymer, the luminescence properties of 4-Eu and 6-Tb are all improved. The results show the best doping concentration is 4%. The thermal stabilities of 4-Eu-PMMA and 6-Tb-PMMA increased from 270 to 315 °C when compared with single coordination polymers 4-Eu and 6-Tb. The co-doping of 4-Eu, 5-Gd, and 6-Tb (0.92/0.04/0.04) with PMMA at a total concentration of 4% resulted in a tunable luminescence material W(4-Eu,5-Gd,6-Tb)-PMMA film. When excited at 285 nm, W(4-Eu,5-Gd,6-Tb

  18. 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.

  19. 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.

  20. DNA damage induced by bare and loaded microporous coordination polymers from their ground and electronic excited states.

    PubMed

    Yañuk, Juan G; Alomar, María L; Gonzalez, M Micaela; Simon, Francisco; Erra-Balsells, Rosa; Rafti, Matías; Cabrerizo, Franco M

    2015-05-21

    We report on interactions of cell free double-stranded DNA (dsDNA) with a selected subgroup of Microporous Coordination Polymers (MCPs). In particular, we have studied the influence of different metal ion constituents and chemically modified linkers using a set of five benzene carboxylate-based MCPs. Our results suggest that the DNA moiety can be structurally modified in two different ways: by direct MCPs-dsDNA interaction and/or through photosensitized processes. The extent of the observed damage was found to be strongly dependent on the charge density of the material. The potential use of the MCPs tested as inert carriers of photosensitizers was demonstrated by analyzing the interaction between dsDNA and harmine-loaded Cr-based materials, both in the absence of light and upon UVA irradiation.

  1. Selective CO2 adsorption in a robust and water-stable porous coordination polymer with new network topology.

    PubMed

    Nagarkar, Sanjog S; Chaudhari, Abhijeet K; Ghosh, Sujit K

    2012-01-02

    A robust and water-stable porous coordination polymer [Cd(NDC)(0.5)(PCA)]·G(x) (1) (H(2)NDC = 2,6-napthalenedicarboxylic acid, HPCA = 4-pyridinecarboxylic acid, G = guest molecules) with new network topology has been synthesized solvothermally. The framework is 3D porous material and forms a 1D channel along the c-axis, with the channel dimensions ~9.48 × 7.83 Å(2). The compound has high selectivity in uptake of CO(2) over other gases (H(2), O(2), Ar, N(2), and CH(4)). The framework is highly stable in presence of water vapor even at 60 °C. The high CO(2) selectivity over other gases and water stability makes the compound promising candidate for industrial postcombustion gas separation application.

  2. 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).

  3. Synthesis, structure and properties of a 3D acentric coordination polymer with noninterpenetrated (10,3)-d topology

    NASA Astrophysics Data System (ADS)

    Lun, Huijie; Li, Xuefei; Wang, Xiao; Li, Haiyan; Li, Yamin; Bai, Yan

    2017-01-01

    A new coordination polymer, {[Mn(HPIDC)(H2O)]·2H2O}n (1) (H3PIDC = 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid), has been obtained by hydrothermal method and structurally characterized by X-ray single crystal diffraction, elemental analysis and thermogravimetric analysis (TGA). X-ray single crystal diffraction reveals that compound 1 crystallizing in acentric Pna21 space group, exhibits an ultimate racemic three-dimension framework with rare noninterpenetrated (10,3)-d (or utp) topology due to the alternate array of left- and right-handed helixes. Moreover, compound 1 also features ferroelectric, nonlinear optical (NLO) and antiferromagnetic behaviors.

  4. Structural diversity and photocatalytic properties of Cd(II) coordination polymers constructed by a flexible V-shaped bipyridyl benzene ligand and dicarboxylate derivatives.

    PubMed

    Liu, Lei-Lei; Yu, Cai-Xia; Ma, Feng-Ji; Li, Ya-Ru; Han, Jing-Jing; Lin, Lu; Ma, Lu-Fang

    2015-01-28

    Hydrothermal reactions of Cd(OAc)2·2H2O with a flexible V-shaped bipyridyl benzene ligand and five benzenedicarboxylic acid derivatives gave rise to five new coordination polymers i.e., [Cd(1,4-BDC)(bpmb)(H2O)]n (1), {[Cd(1,3-BDC)(bpmb)]·0.125H2O}n (2), [Cd2(5-Me-1,3-BDC)2(bpmb)2]n (3), [Cd(5-NO2-1,3-BDC)(bpmb)(H2O)]n (4) and [Cd(5-OH-1,3-BDC)(bpmb)(H2O)]n (5) (bpmb = 1,3-bis(pyridine-3-ylmethoxy)benzene, 1,4-H2BDC = 1,4-benzenedicarboxylic acid, 1,3-H2BDC = 1,3-benzenedicarboxylic acid, 5-Me-1,3-H2BDC = 5-methyl-1,3-benzenedicarboxylic acid, 5-NO2-1,3-H2BDC = 5-nitro-1,3-benzenedicarboxylic acid, 5-OH-1,3-H2BDC = 5-hydroxy-1,3-benzenedicarboxylic acid). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Compound 1 is a two-fold interpenetrating network showing the coexistence of polyrotaxane and polycatenane characters. Compounds 2 and 3 exhibit similar 2D (3,5)-connected (4(2)·6(7)·8)(4(2)·6) nets in which the bpmb ligands work as lockers in interlocking 1D [Cd(1,3-BDC/5-Me-1,3-BDC)]n chains. Compound 4 shows a 2D 4-connected (6(6)) sandwich-like structure with differently oriented [Cd(5-NO2-1,3-BDC)]n chains. Compound 5 is a 3D supramolecular pcu net based on a 1D ladder-shaped chain. These results suggest that the substituted positions of carboxylate groups and changes in substituted R groups in the 5-position of BDC ligands have significant effect on the final structures. These compounds exhibited relatively good photocatalytic activity towards the degradation of methylene blue (MB) in aqueous solution under UV irradiation. Moreover, solid-state photoluminescence properties of 1-5 were also investigated.

  5. Effect of Solvent Molecule in Pore for Flexible Porous Coordination Polymer upon Gas Adsorption and Iodine Encapsulation.

    PubMed

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Taş, Murat; Demiral, Hakan

    2015-12-07

    Four new Zn(II)-coordination polymers, namely, [Zn2(μ6-ao2btc)(μ-obix)2]n (1), [Zn2(μ4-ao2btc)(μ-obix)2]n (2), [Zn2(μ4-ao2btc)(μ-mbix)2]n (3), and {[Zn2(μ4-ao2btc)(μ-pbix)2] · 2DMF · 8H2O}n (4), where ao2btc = dioxygenated form of 3,3',5,5'-azobenzenetetracarboxylate and obix, mbix, and pbix = 1,2-, 1,3-, and 1,4-bis(imidazol-1-ylmethyl)benzene, have been synthesized with azobenzenetetracarboxylic acid and isomeric bis(imidazole) ligands and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analyses. X-ray results showed that 1, 2, and 4 had two-dimensional structures with 3,4L13 topology, while 3 was a three-dimensional coordination polymer with bbf topology. For 4, two types of activation strategies, solvent exchange + heating (which produced 4a) and direct heating (which produced 4b), were used to investigate the effect of a guest molecule in a flexible framework. Gas adsorption and iodine encapsulation properties of activated complexes were studied. The CO2 uptake capacities for 4a and 4b were 3.62% and 9.50%, respectively, and Langmuir surface areas calculated from CO2 isotherms were 167.4 and 350.7 m(2)/g, respectively. Moreover, 4b exhibited 19.65% and 15.27% iodine uptake in vapor phase and cyclohexane solution, respectively, which corresponded to 1.47 and 0.97 molecules of iodine/formula unit, respectively. Moreover, photoluminescence properties of the complexes were studied.

  6. Crystal structures of three lead(II) acetate-bridged di-amino-benzene coordination polymers.

    PubMed

    Geiger, David K; Parsons, Dylan E; Zick, Patricia L

    2014-12-01

    Poly[tris-(acetato-κ(2) O,O')(μ2-acetato-κ(3) O,O':O)tetra-kis-(μ3-acetato-κ(4) O,O':O:O')bis-(benzene-1,2-di-amine-κN)tetra-lead(II)], [Pb4(CH3COO)8(C6H8N2)2] n , (I), poly[(acetato-κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(4-chloro-benzene-1,2-diamine-κN)lead(II)], [Pb(CH3COO)2(C6H7ClN2)] n , (II), and poly[(κ(2) O,O')(μ3-acetato-κ(4) O,O':O:O')(3,4-di-amino-benzo-nitrile-κN)lead(II)], [Pb(CH3COO)2(C7H7N3)] n , (III), have polymeric structures in which monomeric units are joined by bridging acetate ligands. All of the Pb(II) ions exhibit hemidirected coordination. The repeating unit in (I) is composed of four Pb(II) ions having O6, O6N, O7 and O6N coordination spheres, respectively, where N represents a monodentate benzene-1,2-di-amine ligand and O acetate O atoms. Chains along [010] are joined by bridging acetate ligands to form planes parallel to (10-1). (II) and (III) are isotypic and have one Pb(II) ion in the asymmetric unit that has an O6N coordination sphere. Pb2O2 units result from a symmetry-imposed inversion center. Polymeric chains parallel to [100] exhibit hydrogen bonding between the amine and acetate ligands. In (III), additional hydrogen bonds between cyano groups and non-coordinating amines join the chains by forming R 2 (2)(14) rings.

  7. 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.

  8. Synthesis, structure and luminescent properties of rare earth coordination polymers constructed from paddle-wheel building blocks.

    PubMed

    Guo, Xiaodan; Zhu, Guangshan; Fang, Qianrong; Xue, Ming; Tian, Ge; Sun, Jinyu; Li, Xiaotian; Qiu, Shilun

    2005-05-30

    A series of three-dimensional (3D) novel coordination polymers M(bpdc)1.5(H2O) x 0.5DMF (M = Tb (1), Ho (2), Er (3), or Y (4)) have been synthesized by reaction of the rare earth ions (M3+) with 4,4'-biphenyldicarboxylic acid (H2bpdc) in a mixed solution of DMF and C2H5OH. They possess the same 3D architectures and crystallize in monoclinic space group C2/c. Two seven-coordinated metal centers and four dimonodentate bpdc groups construct a paddle-wheel building block. These building blocks connect with two carboxyl groups to lead to a one-dimensional inorganic chain, ---M-O-C-O-M---, along the [001] direction. The inorganic chains are linked with two biphenyl groups to form 25.15 A x 17.09 A rhombic channels along the c axis without interpenetration. These complexes exhibit strong fluorescence in the visible region, and complex 3 shows Er3+ characteristic emission in the range of 1450-1650 nm at room temperature. These complexes could be anticipated as potential fluorescent probes and an IR-emitter, respectively.

  9. White-emissive tandem-type hybrid organic/polymer diodes with (0.33, 0.33) chromaticity coordinates.

    PubMed

    Guo, Tzung-Fang; Wen, Ten-Chin; Huang, Yi-Shun; Lin, Ming-Wei; Tsou, Chuan-Cheng; Chung, Chia-Tin

    2009-11-09

    This study reports fabrication of white-emissive, tandem-type, hybrid organic/polymer light-emitting diodes (O/PLED). The tandem devices are made by stacking a blue-emissive OLED on a yellow-emissive phenyl-substituted poly(para-phenylene vinylene) copolymer-based PLED and applying an organic oxide/Al/molybdenum oxide (MoO(3)) complex structure as a connecting structure or charge-generation layer (CGL). The organic oxide/Al/MoO(3) CGL functions as an effective junction interface for the transport and injection of opposite charge carriers through the stacked configuration. The electroluminescence (EL) spectra of the tandem-type devices can be tuned by varying the intensity of the emission in each emissive component to yield the visible-range spectra from 400 to 750 nm, with Commission Internationale de l'Eclairage chromaticity coordinates of (0.33, 0.33) and a high color rendering capacity as used for illumination. The EL spectra also exhibit good color stability under various bias conditions. The tandem-type device of emission with chromaticity coordinates, (0.30, 0.31), has maximum brightness and luminous efficiency over 25,000 cd/m(2) and approximately 4.2 cd/A, respectively.

  10. Synthesis, crystal structures and properties of three glutarato and adipato bridged manganese(II) coordination polymers under ambient conditions

    NASA Astrophysics Data System (ADS)

    Zheng, Yue-Qing; Zhu, Hong-Lin; Guo, Xia-Xia; Liu, Ji-Yong

    2013-04-01

    Three Mn(II) polymers Mn(H2O)4(C5H6O4) 1, [Mn(H2O)2(C5H6O4)]·H2O 2 and Mn(H2O)(C6H8O4) 3 were synthesized (H2(C5H6O4) = glutaric acid, H2(C6H8O4) = adipic acid) under mild ambient conditions. The [Mn(H2O)2]2+ units in 2 are interlinked by the glutarate anions with a η4μ3 bridging mode to form 2D (4·82) topological networks, which are stacked via interlayer hydrogen bonds into a 3D (43·65·82)(47·63) topological net. Compound 3 crystallizes in the acentric space group P21 and exhibits significant ferroelectricity (remnant polarization Pr = 0.371 nC cm-2, coercive field Ec = 0.028 kV cm-1, saturation of the spontaneous polarization Ps = 0.972 nC cm-2). The adjacent MnO6 octahedrons in 3 are one atom-shared to generate the Mn2O11 bi-octahedron, leading into 1D metal oxide chains. The resulting chains are interconnected by the η5μ5 adipate anions to form new 2D (48·62) networks, which are held together via strong interlayer hydrogen bonds into 3D α-Po topological supra-molecular architecture. The temperature-dependent magnetic susceptibility data of 1-3 shows overall anti-ferromagnetic interactions between the metal ions bridged by the carboxylate groups.

  11. 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.

  12. Three Pb{sup II} coordination polymers based on 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid: Syntheses, crystal structures, and fluorescent properties

    SciTech Connect

    Yu, Xiao-Yang; Xin, Rui; Gao, Wei-Ping; Wang, Na; Zhang, Xiao; Yang, Yan-Yan; Qu, Xiao-Shu

    2013-08-15

    Three lead coordination polymers, [PbCl(C{sub 10}H{sub 6}N{sub 3}O{sub 4})(H{sub 2}O)·H{sub 2}O]{sub n} (1), [Pb(C{sub 10}H{sub 6}N{sub 3}O{sub 4}){sub 2}(H{sub 2}O)]{sub n} (2) and [Pb{sub 3}(C{sub 10}H{sub 5}N{sub 3}O{sub 4}){sub 3}]{sub n} (3) (C{sub 10}H{sub 7}N{sub 3}O{sub 4}=2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. In 1, Cl anions connected neighboring wave-like 2D layers, which are constructed with left- and right-handed helical chains, into a 3D network structure with a (6{sup 3})(6{sup 5}·8) topology. In 2, Pb cations are linked into a 3D 6{sup 6} network with left- and right-handed helixes by μ{sub 2}-bridging C{sub 10}H{sub 6}N{sub 3}O{sub 4}{sup −} ligands. In 3, C{sub 10}H{sub 5}N{sub 3}O{sub 4}{sup 2−} ligands link Pb{sub 6}O{sub 12} clusters into a 3D (4{sup 12}·6{sup 3}) network. Their fluorescent properties were also investigated. - Graphical abstract: Three 3D lead compounds based on 2-(pyridin-2-yl)-1H-imidazole-4,5-dicarboxylic acid have been hydrothermally synthesized. Four new coordination modes of the organic ligand are first reported. Display Omitted - Highlights: • Three new Pb(II) complexes have been synthesized and characterized. • Left- and right-handed helical chains can be found in the 3D networks of 1 and 2. • Pb{sub 6}O{sub 12} clusters are connected into (4{sup 12}·6{sup 3}) network in 3.

  13. H2, N2, CO, and CO2 sorption properties of a series of robust sodalite-type microporous coordination polymers.

    PubMed

    Navarro, Jorge A R; Barea, Elisa; Salas, Juan M; Masciocchi, Norberto; Galli, Simona; Sironi, Angelo; Ania, Conchi O; Parra, José B

    2006-03-20

    H2, N2, CO, and CO2 are readily incorporated in the porous, 3D sodalitic frameworks of coordination polymers of the [ML2]n type, with M = Pd(II) or Cu(II) and HL = 2-hydroxypyrimidine or 4-hydroxypyrimidine. The metal ion and ligand functionalization modulate their sorption properties, making these materials suitable for gas storage and separation purposes.

  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. 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).

  17. Synthesis, structure and dielectric properties of a Cd coordination polymer based on homopiperazine

    NASA Astrophysics Data System (ADS)

    Shi, Qiu-Zhong; Xing, Zheng; Cao, Yong-Nan; Ma, Shi-Bing; Chen, Li-Zhuang

    2017-02-01

    A (4,6)-connected three-dimensional network complex [Cd(hpip)Br2]n (1) [hpip = homopiperazine] was prepared from CdBr2·4H2O and hpip by hydrothermal reaction in water. The structure was characterized by single-crystal X-ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis and elemental analysis. The asymmetric unit contains one hpip ligand, one Cd(II) cation and two Br- anions. Each Cd(II) cation is coordinated by two N atoms from the ligand and four Br- anions, showing a distorted octahedral geometry. Its dielectric constant was measured at different frequencies with temperature variations.

  18. Design and solvothermal synthesis of luminescent copper(I)-pyrazolate coordination oligomer and polymer frameworks.

    PubMed

    He, Jun; Yin, Ye-Gao; Wu, Tao; Li, Dan; Huang, Xiao-Chun

    2006-07-21

    Two luminescent coordination compounds, [Cu(Pz)]3 (1) and [Cu2(Bpz)]n (2), were isolated from solvothermal reactions of Cu(NO3)2 with 3,5-dimethylpyrazole (HPz) and 3,3',5,5'-tetra-methyl-4,4'-bipyrazole (H2Bpz) respectively in the presence of NH3, of which 1 was revealed to be a planar trimer and 2 a three-dimensional framework, presenting a rare 3-connected binodal (6(2).10)(6.10(2)) topology and eight-fold interpenetration.

  19. 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.

  20. (infinity)(2)[Cu2(mu5-btb)(mu-OH)(mu-H2O)]: a two-dimensional coordination polymer built from ferromagnetically coupled Cu2 units (btb = benzene-1,2,3-tricarboxylate).

    PubMed

    Habib, Hesham A; Sanchiz, Joaquin; Janiak, Christoph

    2008-09-28

    Hydrothermal reaction of Cu(NO3)(2).3H2O, Cd(OH)2 or Zn(OH)2 with benzene-1,2,3-tricarboxylic acid (H3btb, hemimellitic acid) produced the 2D coordination polymer (MOF) (infinity)(2)[Cu2(mu5-btb)(mu-OH)(mu-H2O)] (1) and the 2D hydrogen-bonded complexes [Cd(H2btb)2(H2O)4].2H2O (2) and [Zn(H2O)6](H2btb)(2).4H2O (3) which are characterized by single-crystal X-ray diffraction, X-ray powder diffraction and thermoanalysis. Magnetic susceptibility measurements between 1.9-300 K for 1 revealed three magnetic active exchange pathways that link the copper(II) ions through a long mu-aqua bridge, an anti-syn carboxylate bridge [j2 = 0.161(1) cm(-1)], and through a mixed mu-hydroxo + syn-syn carboxylate bridge [J = 83(1) cm(-1)]. At temperatures higher than 30 K the system behaves as isolated Cu2 units with strong ferromagnetic Cu-Cu coupling through the mu-hydroxo and syn-syn carboxylate bridge. The strong ferromagnetic coupling is explained with Hoffmann's approach by means of the concept of counter-complementarity introduced by Nishida et al.[Chem. Lett., 1983, 1815-1818].

  1. Synthesis of a new Cd(II)-Ni(II) hetero-metallic coordination polymer base on citric acid ligand. X-ray structure, thermal stability, XPS and fluorescence studies

    NASA Astrophysics Data System (ADS)

    Mtioui-Sghaier, O.; Mendoza-Meroño, R.; Fernández-Zapico, E.; García-Granda, S.; Fernández-González, A.; Ktari, L.; Dammak, M.

    2016-02-01

    A new hetero-metallic polymer, NiCd(cit)(H2O) (cit = citrate), was synthesized under hydrothermal conditions. The structural analysis indicates the formation of a 2D structure, bridged by the cit4- group. This compound crystallizes in the monoclinic P21/c space group, with lattice parameters: a = 6.0817(3) Å, b = 14.9725(6) Å, c = 9.6817(5) Å, β = 101.353(5)°. Full characterization by powder diffraction analysis, thermocalorimetry and scanning electron microscopy, XPS and fluorescence have been carried out. The TG-MS and DSC results show that this compound is thermally stable up to 250 °C and the DSC profile shows a medium-intense endotherm centred at approximately 300 °C. The distances of Cd-O are in the range of 2.169(4)-2.647(4) Å, similar to pure cadmium(II)-citrate aqueous complex Cd(C6H6O7)(H2O). The six-coordinated Cd2+ is linked by carboxylate groups to form an infinite chain, which is further connected through NiO6 octahedral bridges to generate 2D structure in the bc plane.

  2. 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.

  3. 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

    2014-09-08

    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.

  4. Solvent-regulated assemblies of four Zn(II) coordination polymers constructed by flexible tetracarboxylates and pyridyl ligands

    NASA Astrophysics Data System (ADS)

    Fang, Kang; He, Xiang; Shao, Min; Li, Ming-Xing

    2016-08-01

    Four unique complexes with diverse coordination architectures were synthesized upon complexation of 5,5-(1,4-phenylenebis (methylene))bis (oxy)- diisophthalic acid (H4L) with zinc ions by using different solvent. namely, {[Zn(H2L) (bpp)]·DEF}n (1), {[Zn2(L) (bpp)2]·4H2O}n (2), {[Zn2(L) (pdp)2]·3H2O·DEF}n (3), {[Zn2(L) (pdp)2].4H2O}n (4). Complexes 1,2 and 3,4 are obtained by varying solvents to control their structures. The size of solvent molecular plays an important role to control different structure of these compounds. Compound 1 is 2D waved framework with (4, 4) grid layer as sql topology. Compound 3 displays a (4,6)-connected 2-nodal net with a fsc topology. Compounds 2 and 4 are all three-dimensional network simplified as (4,4)-connected 2-nodal net with a bbf topology. The photochemical properties of compounds 1-4 were tested in the solid state at room temperature, owing to their strong luminescent emissions, complexes 1-4 are good candidates for photoactive materials.

  5. 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.

  6. A versatile solvent-free mechanochemical route to the synthesis of heterometallic dicyanoaurate-based coordination polymers.

    PubMed

    Jobbágy, Csaba; Tunyogi, Tünde; Pálinkás, Gábor; Deák, Andrea

    2011-08-01

    The solid-state mechanochemical method was proved to be a fast, simple, and efficient route to the synthesis of heterometallic [Au(CN)(2)]-based coordination polymers. Thus, a series of mixed-metal complexes, such as KCo[Au(CN)(2)](3), KNi[Au(CN)(2)](3), Cu(H(2)O)(2)[Au(CN)(2)](2), and Zn[Au(CN)(2)](2), was obtained by grinding stoichiometric amounts of K[Au(CN)(2)] and transition metal(II) chlorides. This solid-state method rapidly yields pure dicyanoaurate-based compounds, also in cases when the aqueous solution synthesis leads to an unseparable mixture of products. In addition, in some cases, the solid state reaction was faster than the corresponding solvent-based reaction. This mechanochemical method can be applied also to main group metals to obtain various cyanoaurate-based heterometallic coordination polymers, such as Me(2)Sn[Au(CN)(2)](2) and Ph(3)Sn[Au(CN)(2)]. For the 2:1 mixture of K[Au(CN)(2)] and Me(2)SnCl(2), the dramatic enhancement of the reaction rate by the presence of a minor amount of water was noticed. In Ph(3)Sn[Au(CN)(2)], as was revealed by single-crystal X-ray diffraction, each Ph(3)Sn unit is linked to two others by two Au(CN)(2) bridges via Sn-N bonds to form an infinite cyanide-bridged chain. There are no Au···Au contacts between the chains due to the sterical hindrance of the phenyl groups. A dehydrated blue Co[Au(CN)(2)](2) complex was obtained during grinding or heating of the moderate-pink Co(H(2)O)(2)[Au(CN)(2)](2) complex. This complex displays a vapochromic response when exposed to a variety of organic solvents, as well as water and ammonia vapors.

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    The organic ligand 2,5-piperazinedione-1,4-diacetic acid (H2PDA) 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 P21/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 P21/n monoclinic system with chemical formula [Ln(PDA)1.5(H2O)](H2O)3 (Ln=Gd3+(1) and Eu3+(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.

  8. 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.

  9. Influence of conformational flexibility on self-assembly and luminescence properties of lanthanide coordination polymers with flexible exo-bidentate biphenol derivatives.

    PubMed

    Guo, Yanling; Dou, Wei; Zhou, Xiaoyan; Liu, Weisheng; Qin, Wenwu; Zang, Zhipeng; Zhang, Hongrui; Wang, Daqi

    2009-04-20

    To explore how nonplanar conformational distortions affect supramolecular self-assembly and properties of lanthanide complexes, we have designed and synthesized two new flexible exo-bidentate ligands derived from biphenol featuring two salicylamide pendant arms, 2,2'-bis{[(2'-benzylaminoformyl)phenoxyl]ethoxyl}-1,1'-biphenylene (L(I)) and 5,5'-dibromo-2,2'-bis{[(2'-benzylaminoformyl)phenoxyl]ethoxyl}-1,1'-biphenylene (L(II)). These two structurally related ligands can have different conformations and are used for constructing diverse lanthanide polymers with interesting luminescence properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, X-ray powder diffraction, and IR spectroscopy, four new coordination polymers have been determined using X-ray diffraction analysis. The coordination polymer type {Ln(2)(NO(3))(6)(L(I))(3).3H(2)O}(infinity) (Ln = Nd, Sm, Eu, Gd, Tb or Dy) displays a two-dimensional honeycomb-like framework in the ab plane, which can be regarded as a (6,3) topological network with neodymium atoms acting as "three-connected" centers. In contrast, the coordination polymer types {[Nd(NO(3))(3)(L(II))(CH(3)OH)] x CH(3)OH}(infinity) and [Ln(NO(3))(3)(L(II))(C(2)H(5)OH)](infinity) (Ln = Sm, Eu, Gd, Tb or Dy) possess single-stranded helix chains which can be further connected through intermolecular hydrogen bonds to form two-dimensional supramolecular sheets. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were investigated. The present work substantiates the claim that the supramolecular structure as well as the luminescence properties of the coordination polymer can be tuned by controlling the conformational distortion of a nonplanar flexible ligand in the supramolecular self-assembly.

  10. Vertical 2D Heterostructures

    NASA Astrophysics Data System (ADS)

    Lotsch, Bettina V.

    2015-07-01

    Graphene's legacy has become an integral part of today's condensed matter science and has equipped a whole generation of scientists with an armory of concepts and techniques that open up new perspectives for the postgraphene area. In particular, the judicious combination of 2D building blocks into vertical heterostructures has recently been identified as a promising route to rationally engineer complex multilayer systems and artificial solids with intriguing properties. The present review highlights recent developments in the rapidly emerging field of 2D nanoarchitectonics from a materials chemistry perspective, with a focus on the types of heterostructures available, their assembly strategies, and their emerging properties. This overview is intended to bridge the gap between two major—yet largely disjunct—developments in 2D heterostructures, which are firmly rooted in solid-state chemistry or physics. Although the underlying types of heterostructures differ with respect to their dimensions, layer alignment, and interfacial quality, there is common ground, and future synergies between the various assembly strategies are to be expected.

  11. 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.

  12. Synthetic Architecture of MgO/C Nanocomposite from Hierarchical-Structured Coordination Polymer toward Enhanced CO2 Capture.

    PubMed

    Li, Ping; Liu, Wen; Dennis, John S; Zeng, Hua Chun

    2017-03-22

    Highly efficient, durable, and earth-abundant solid sorbents are of paramount importance for practical carbon capture, storage, and utilization. Here, we report a novel and facile two-step strategy to synthesize a group of hierarchically structured porous MgO/C nanocomposites using flowerlike Mg-containing coordination polymer as a precursor. The new nanocomposites exhibit superb CO2 capture performance with sorption capacity up to 30.9 wt % (at 27 °C, 1 bar CO2), fast sorption kinetics, and long cycling life. Importantly, the achieved capacity is >14 times higher than that of commercial MgO, and favorably exceeds the highest value recorded to date for MgO-based sorbents under similar operating conditions. On the basis of the morphological and textural property analysis, together with CO2 sorption mechanism study using CO2-TPD and DRIFT techniques, the outstanding performance in CO2 uptake originates from unique features of this type of sorbent materials, which include hierarchical architecture, porous building blocks of nanosheets, high specific surface area (ca. 300 m(2)/g), evenly dispersed MgO nanocrystallites (ca. 3 nm) providing abundant active sites, and the in situ generated carbon matrix that acts as a stabilizer to prevent the growth and agglomeration of MgO crystallites. The nanocomposite system developed in this work shows good potential for future low-cost CO2 abatement and utilization.

  13. 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.

  14. 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

  15. 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.

  16. Integration of porous coordination polymers and gold nanorods into core-shell mesoscopic composites toward light-induced molecular release.

    PubMed

    Khaletskaya, Kira; Reboul, Julien; Meilikhov, Mikhail; Nakahama, Masashi; Diring, Stéphane; Tsujimoto, Masahiko; Isoda, Seiji; Kim, Franklin; Kamei, Ken-ichiro; Fischer, Roland A; Kitagawa, Susumu; Furukawa, Shuhei

    2013-07-31

    Besides conventional approaches for regulating in-coming molecules for gas storage, separation, or molecular sensing, the control of molecular release from the pores is a prerequisite for extending the range of their application, such as drug delivery. Herein, we report the fabrication of a new porous coordination polymer (PCP)-based composite consisting of a gold nanorod (GNR) used as an optical switch and PCP crystals for controlled molecular release using light irradiation as an external trigger. The delicate core-shell structures of this new platform, composed of an individual GNR core and an aluminum-based PCP shell, were achieved by the selective deposition of an aluminum precursor onto the surface of GNR followed by the replication of the precursor into aluminum-based PCPs. The mesoscopic structure was characterized by electron microscopy, energy dispersive X-ray elemental mapping, and sorption experiments. Combination at the nanoscale of the high storage capacity of PCPs with the photothermal properties of GNRs resulted in the implementation of unique motion-induced molecular release, triggered by the highly efficient conversion of optical energy into heat that occurs when the GNRs are irradiated into their plasmon band. Temporal control of the molecular release was demonstrated with anthracene as a guest molecule and fluorescent probe by means of fluorescence spectroscopy.

  17. 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.

  18. Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

    PubMed Central

    Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

    2014-01-01

    Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior. PMID:25113225

  19. Impact of metallophilicity on "colossal" positive and negative thermal expansion in a series of isostructural dicyanometallate coordination polymers.

    PubMed

    Korcok, Jasmine L; Katz, Michael J; Leznoff, Daniel B

    2009-04-08

    Five isostructural dicyanometallate coordination polymers containing metallophilic interactions (In[M(CN)(2)](3) (M = Ag, Au), KCd[M(CN)(2)](3), and KNi[Au(CN)(2)](3)) were synthesized and investigated by variable-temperature powder X-ray diffraction to probe their thermal expansion properties. The compounds have a trigonal unit cell and show positive thermal expansion (PTE) in the ab plane, where Kagome sheets of M atoms reside, and negative thermal expansion (NTE) along the trigonal c axis, perpendicular to these sheets. The magnitude of thermal expansion is unusually large in all cases (40 x 10(-6) K(-1) < |alpha| < 110 x 10(-6) K(-1)). The system with the weakest metallophilic interactions, In[Ag(CN)(2)](3), shows the most "colossal" thermal expansion of the series (alpha(a) = 105(2) x 10(-6) K(-1), alpha(c) = -84(2) x 10(-6) K(-1) at 295 K), while systems containing stronger Au-Au interactions show relatively reduced thermal expansion. Thus, it appears that strong metallophilic interactions hinder colossal thermal expansion behavior. Additionally, the presence of K(+) counterions also reduces the magnitude of thermal expansion.

  20. Silver Coordination Polymers for Prevention of Implant Infection: Thiol Interaction, Impact on Respiratory Chain Enzymes, and Hydroxyl Radical Induction▿ †

    PubMed Central

    Gordon, Oliver; Vig Slenters, Tünde; Brunetto, Priscilla S.; Villaruz, Amer E.; Sturdevant, Daniel E.; Otto, Michael; Landmann, Regine; Fromm, Katharina M.

    2010-01-01

    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. PMID:20660682

  1. "Dual-template" synthesis of one-dimensional conductive nanoparticle superstructures from coordination metal-peptide polymer crystals.

    PubMed

    Rubio-Martínez, Marta; Puigmartí-Luis, Josep; Imaz, Inhar; Dittrich, Petra S; Maspoch, Daniel

    2013-12-20

    Bottom-up fabrication of self-assembled structures made of nanoparticles may lead to new materials, arrays and devices with great promise for myriad applications. Here a new class of metal-peptide scaffolds is reported: coordination polymer Ag(I)-DLL belt-like crystals, which enable the dual-template synthesis of more sophisticated nanoparticle superstructures. In these biorelated scaffolds, the self-assembly and recognition capacities of peptides and the selective reduction of Ag(I) ions to Ag are simultaneously exploited to control the growth and assembly of inorganic nanoparticles: first on their surfaces, and then inside the structures themselves. The templated internal Ag nanoparticles are well confined and closely packed, conditions that favour electrical conductivity in the superstructures. It is anticipated that these Ag(I)-DLL belts could be applied to create long (>100 μm) conductive Ag@Ag nanoparticle superstructures and polymetallic, multifunctional Fe3 O4 @Ag nanoparticle composites that marry the magnetic and conductive properties of the two nanoparticle types.

  2. 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.

  3. 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.

  4. Colorimetric and Fluorescent Dual Mode Sensing of Alcoholic Strength in Spirit Samples with Stimuli-Responsive Infinite Coordination Polymers.

    PubMed

    Deng, Jingjing; Ma, Wenjie; Yu, Ping; Mao, Lanqun

    2015-07-07

    This study demonstrates a new strategy for colorimetric and fluorescent dual mode sensing of alcoholic strength (AS) in spirit samples based on stimuli-responsive infinite coordination polymers (ICPs). The ICP supramolecular network is prepared with 1,4-bis(imidazol-1-ylmethyl)benzene (bix) as the ligand and Zn(2+) as the central metal ion in ethanol, in which rhodamine B (RhB) is encapsulated through self-adaptive chemistry. In pure ethanol solvent, the as-formed RhB/Zn(bix) is well dispersed and quite stable. However, the addition of water into the ethanol dispersion of RhB/Zn(bix) destroys Zn(bix) network structure, resulting in the release of RhB from ICP into the solvent. As a consequence, the solvent displays the color of released RhB and, at the meantime, turns on the fluorescence of RhB, which constitutes a new mechanism for colorimetric and fluorescent dual mode sensing of AS in commercial spirit samples. With the method developed here, we could distinguish the AS of different commercial spirit samples by the naked eye within a wide linear range from 20 to 100% vol and by monitoring the increase of fluorescent intensity of the released RhB. This study not only offers a new method for on-spot visible detection of AS in commercial spirit samples, but also provides a strategy for designing dual mode sensing mechanisms for different analytical purposes based on novel stimuli-responsive materials.

  5. Al-Based coordination polymer nanotubes: simple preparation, post-modification and application in Fe(3+) ions sensing.

    PubMed

    Dao, Xiaoyao; Ni, Yonghong

    2017-04-06

    Aluminum-based coordination polymers, MIL-110(Al) nanotubes, were successfully prepared from a mixed solution of methanol and ethanol with the volume ratio of 10 : 10 at room temperature in the absence of any template or surfactant; AlCl3 and sodium 1,3,5-benzenetricarboxylate (Na3BTC) were employed as the initial reactants. The composition, structure, and morphology of the as-obtained nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). It was found that the initial reaction medium played a crucial role in the formation of nanotubes. More importantly, MIL-110(Al) nanotubes could be fabricated into lanthanide-functionalized luminescent materials by a simple post-treatment process. The as-obtained luminescent materials could emit red, green, and white light, which have potential applications in the fields of sensing, biomedicine, labeling, and color display. Furthermore, the PL of the as-obtained luminescent materials could be selectively quenched by Fe(3+) ions, which can be used as probes for the detection of Fe(3+) ions.

  6. Nanorods of a new metal-biomolecule coordination polymer showing novel bidirectional electrocatalytic activity and excellent performance in electrochemical sensing.

    PubMed

    Yang, Jiao; Zhou, Bo; Yao, Jie; Jiang, Xiao-Qing

    2015-05-15

    Metal organic coordination polymers (CPs), as most attractive multifunctional materials, have been studied extensively in many fields. However, metal-biomolecule CPs and CPs' electrochemical properties and applications were studied much less. We focus on this topic aiming at electrochemical biosensors with excellent performance and high biocompatibility. A new nanoscaled metal-biomolecule CP, Mn-tyr, containing manganese and tyrosine, was synthesized hydrothermally and characterized by various techniques, including XRD, TEM, EDS, EDX mapping, elemental analysis, XPS, and IR. Electrode modified with Mn-tyr showed novel bidirectional electrocatalytic ability toward both reduction and oxidation of H2O2, which might be due to Mn. With the assistance of CNTs, the sensing performance of Mn-tyr/CNTs/GCE was improved to a much higher level, with high sensitivity of 543 mA mol(-1) L cm(-2) in linear range of 1.00×10(-6)-1.02×10(-4) mol L(-1), and detection limit of 3.8×10(-7) mol L(-1). Mn-tyr/CNTs/GCE also showed fast response, high selectivity, high steadiness and reproducibility. The excellent performance implies that the metal-biomolecule CPs are promising candidates for using in enzyme-free electrochemical biosensing.

  7. Alkaline earth complexes of silylated aminopyridinato ligands: homoleptic compounds and heterobimetallic coordination polymers.

    PubMed

    Ortu, Fabrizio; Moxey, Graeme J; Blake, Alexander J; Lewis, William; Kays, Deborah L

    2013-11-04

    The synthesis and characterization of magnesium and calcium complexes of sterically demanding aminopyridinato ligands is reported. The reaction of the 2-Me3SiNH-6-MeC5H3N (L(1)H), 2-MePh2SiNH-6-MeC5H3N (L(2)H), and 2-Me3SiNH-6-PhC5H3N (L(3)H) with KH in tetrahydrofuran (THF) yielded potassium salts L(1)K(thf)0.5 (1), L(2)K (2), and L(3)K(thf)0.5 (3), which, through subsequent reaction with MgI2 and CaI2, afforded the homoleptic complexes (L)2Ae(thf)n [L = L(1), Ae = Mg, n = 1 (4); L = L(2), Ae = Mg, n = 0 (5); L = L(3), Ae = Mg, n = 0 (6); L = L(2), Ae = Ca, n = 2 (7)] and heterobimetallic calciates {[(L)3Ca]K}∞ [L = L(1) (8); L = L(2) (9)]. The solid state structure of 8 reveals a polymeric arrangement in which the calciate units are interlocked by bridging potassium ions. Metalation reactions between L(1)H or L(2)H and ((n)Bu)2Mg lead to the solvent-free compounds (L)2Mg [L = L(1) (10); L = L(2) (5)]. The bridged butyl mixed-metal complex [(L(1))Li(μ2-(n)Bu)Mg(L(1))]∞ (11) was also obtained via a cocomplexation reaction with (n)BuLi and ((n)Bu)2Mg. 11, which adopts a monodimensional polymeric array in the solid state, is a rare example of an alkyl-bridged Li/Mg complex and the first complex to feature an unsupported bridging butyl interaction between two metals. Changing the cocomplexation reaction conditions, the order of reagents added to the reactions mixture, and with the use of a coordinating solvent (tetrahydrofuran) formed the magnesiate complex (L(1))3MgLi(thf) (12).

  8. Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Zhang, Jinfang; Wang, Chao; Wang, Yinlin; Chen, Weitao; Cifuentes, Marie P.; Humphrey, Mark G.; Zhang, Chi

    2015-11-01

    The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr4N][WS4Cu3(CN)2]}n (1), {[Pr4N][WS4Cu4(CN)3]}n (2), {[Pr4N][WOS3Cu3(CN)2]}n (3), {[Bu4N][WOS3Cu3(CN)2]}n (4) and {[Bu4N][MoOS3Cu3(CN)2]}n (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS4Cu3]+ and single CN- bridges. 2 is fabricated from 6-connected planar 'open' clusters [WS4Cu4]2+ and single CN- bridges, forming an anionic 3D architecture with an "ACS" topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS3Cu3]+ linked by single CN- bridges, but containing the different cations [Pr4N]+ and [Bu4N]+, respectively. 5 is constructed from nest-shaped clusters [MoOS3Cu3]+ and single CN- bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN- bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr4N]+ vs. [Bu4N]+) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2 exhibits effective photocatalytic properties.

  9. 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.

  10. Utilizing bifurcated halogen-bonding interactions with the uranyl oxo group in the assembly of a UO2-3-bromo-5-iodobenzoic acid coordination polymer.

    PubMed

    Kalaj, Mark; Carter, Korey P; Cahill, Christopher L

    2017-04-01

    The synthesis and crystal structure of a new uranyl coordination polymer featuring 3-bromo-5-iodobenzoic acid is described and the luminescent and vibrational properties of the material have been explored. Compound (1), [UO2(C7H3BrIO2)2]n, features dimeric uranyl units chelated and then linked by 3-bromo-5-iodobenzoic acid ligands to form a one-dimensional coordination polymer that is subsequently assembled via bifurcated halogen-bonding interactions with uranyl oxo atoms to form a supramolecular three-dimensional network. The asymmetric, bifurcated halogen-bonding interaction in (1) is notable as it represents the first observation of this synthon in a uranyl hybrid material. Raman and IR spectroscopy showed that halogen-bonding interactions with the uranyl oxo atoms result in small shifts in υ1 and υ3 frequencies, whereas luminescence spectra collected at an excitation wavelength of 420 nm reveal partially resolved uranyl emission.

  11. Studies on the relation between the size and dispersion of metallic silver nanoparticles and morphologies of initial silver(I) coordination polymer precursor

    NASA Astrophysics Data System (ADS)

    Moradi, Zhaleh; Akhbari, Kamran; Phuruangrat, Anukorn; Costantino, Ferdinando

    2017-04-01

    Micro and nano-structures of [Ag2(μ2-dcpa)2]n (1), [Hdcpa = 2,4-dichlorophenoxyacetic acid] which is a one-dimensional coordination polymer with corrugated tape chains, were synthesized as the bulk sample (1B), by sonochemical process (1S) and from mechanochemical reaction (1M). These three samples have been used as new precursors for fabricating silver nanoparticles via direct calcination at 300 °C and also thermal decomposition in oleic acid (OA) as a surfactant at 180 °C. In the presence of OA less agglomerated nanostructures were formed. It seems that the size, dispersion, morphology and agglomeration of initial precursor have direct influence on size, dispersion, morphology and agglomeration of metallic silver. This coordination polymer with various micro and nano morphologies were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Thermal stability of these samples were studied and compared with each other, too.

  12. 2D semiconductor optoelectronics

    NASA Astrophysics Data System (ADS)

    Novoselov, Kostya

    The advent of graphene and related 2D materials has recently led to a new technology: heterostructures based on these atomically thin crystals. The paradigm proved itself extremely versatile and led to rapid demonstration of tunnelling diodes with negative differential resistance, tunnelling transistors, photovoltaic devices, etc. By taking the complexity and functionality of such van der Waals heterostructures to the next level we introduce quantum wells engineered with one atomic plane precision. Light emission from such quantum wells, quantum dots and polaritonic effects will be discussed.

  13. Three dimensional nano-assemblies of noble metal nanoparticle-infinite coordination polymers as specific oxidase mimetics for degradation of methylene blue without adding any cosubstrate.

    PubMed

    Wang, Lihua; Zeng, Yi; Shen, Aiguo; Zhou, Xiaodong; Hu, Jiming

    2015-02-07

    Novel three-dimensional (3D) nano-assemblies of noble metal nanoparticle (NP)-infinite coordination polymers (ICPs) are conveniently fabricated through the infiltration of HAuCl4 into hollow Au@Ag@ICPs core-shell nanostructures and its replacement reaction with Au@Ag NPs. The present 3D nano-assemblies exhibit highly efficient and specific intrinsic oxidase-like activity even without adding any cosubstrate.

  14. 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

    2014-11-04

    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.

  15. 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)

  16. 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.

  17. The Diphosphorus Complex [Cp2Mo2(CO)4(η2‐P2)] as a Building Block for the Synthesis of Mixed‐Hybrid Coordination Polymers

    PubMed Central

    Moussa, Mehdi Elsayed; Attenberger, Bianca; Fleischmann, Martin; Schreiner, Andrea

    2016-01-01

    The three‐component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η2‐P2)] (1), with Ag[BF4] (2) in the presence of 2,2′‐bipyrimidine (3) leads to the formation of the two novel two‐dimensional networks 4 and 5. Compound 4 is a new two‐dimensional organometallic‐organic hybrid polymer, while derivative 5 represents a unique two‐dimensional organometallic‐inorganic‐organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two‐component reactions with organic molecules in addition of metal ions. PMID:27867315

  18. 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

    2015-01-02

    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.

  19. A bridge between pillared-layer and helical structures: a series of three-dimensional pillared coordination polymers with multiform helical chains.

    PubMed

    Xiao, Dong-Rong; Wang, En-Bo; An, Hai-Yan; Li, Yang-Guang; Su, Zhong-Min; Sun, Chun-Yan

    2006-08-25

    Rational self-assembly of a long V-shaped 3,3',4,4'-benzophenonetetracarboxylate (bptc) ligand and metal salts in the presence of linear bidentate ligand yield a series of novel pillared helical-layer complexes, namely, [Cu2(bptc)(bpy)2] (1), [M3(Hbptc)2(bpy)3(H2O)4].2 H2O (M = Fe(2) and Ni(3)), [Co2(bptc)(bpy)(H2O)].0.5 bpy (4), [Cd2(bptc)(bpy)(H2O)2].H2O (5), [Mn2(bptc)(bpy)1.5(H2O)3] (6) and [M2(bptc)(bpy)0.5(H2O)5].0.5 bpy (M = Mn(7), Mg(8) and Co(9), bpy=4,4'-bipyridine). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. The structure of 1 consists of two types of chiral layers, one left-handed and the other right-handed, which are connected by bpy pillars to generate a novel 3D open framework featuring four distinct helical chains. Compounds 2 and 3 are isostructural and feature 3D structures formed from the interconnection of arm-shaped helical layers with bpy pillars. Compound 4 is a pillared helical double-layer complex containing four different types of helices, among which the nine-fold interwoven helices constructed from triple-stranded helical motifs are unprecedented. Compound 5 exhibits a novel 3D covalent framework which features nanosized tubular channels. These channels are built from helical layers pillared by bptc ligands. The structure of 6 is constructed from {Mn(bptc)(H2O)}n2n- layers, which consist of left- and right-handed helical chains, pillared by [Mn2(bpy)3(H2O)4]4+ complexes into a 3D framework. To the best of our knowledge, compounds 1-6 are the first examples of pillared helical-layer coordination polymers. Compounds 7-9 are isostructural and exhibit interesting 2D helical double-layer structures, which are constructed from {M(bptc)(H2O)2}n2n- ribbons cross-linked by [M2(bpy)(H2O)6]4+ complexes. Furthermore, the 3D supramolecular structures of 7-9 are similar to the 3D structure of 6, and the 2D structure of 7

  20. To What Degree Does Handling Concrete Molecular Models Promote the Ability to Translate and Coordinate between 2D and 3D Molecular Structure Representations? A Case Study with Algerian Students

    ERIC Educational Resources Information Center

    Mohamed-Salah, Boukhechem; Alain, Dumon

    2016-01-01

    This study aims to assess whether the handling of concrete ball-and-stick molecular models promotes translation between diagrammatic representations and a concrete model (or vice versa) and the coordination of the different types of structural representations of a given molecular structure. Forty-one Algerian undergraduate students were requested…