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Sample records for magnetochemistry

  1. Reflection spectra and magnetochemistry of iron oxides and natural surfaces

    NASA Technical Reports Server (NTRS)

    Wasilewski, P.

    1978-01-01

    The magnetic properties and spectral characteristics of iron oxides are distinctive. Diagnostic features in reflectance spectra (0.5 to 2.4 micron) for alpha Fe2O3, gamma Fe2O3, and FeOOH include location of Fe3(+) absorption features, intensity ratios at various wavelengths, and the curve shape between 1.2 micron and 2.4 micron. The reflection spectrum of natural rock surfaces are seldom those of the bulk rock because of weathering effects. Coatings are found to be dominated by iron oxides and clay. A simple macroscopic model of rock spectra (based on concepts of stains and coatings) is considered adequate for interpretation of LANDSAT data. The magnetic properties of materials associated with specific spectral types and systematic changes in both spectra and magnetic properties are considered.

  2. Solid state and magnetochemistry of the SrO-Fe2O3 system IV. Synthesis of SrFe12O19 from coprecipitated precursors

    NASA Astrophysics Data System (ADS)

    Qian, Xueyu; Evans, B. J.

    1981-03-01

    By means of 57Fe Mössbauer spectroscopy and powder x-ray diffraction techniques, it has been determined that the formation of SrFe12O19 from coprecipitated ferric hydroxide and strontium laurate follows a reaction mechanism different from that when SrCO3 and Fe2O3 are used as starting materials. Upon heating at 300 C in vacuum, strontium laurate decomposes and further heating to 550 C leads to the formation of γ-Fe2O3 from the ferric hydroxide and solid solution of SrO in γ-Fe2O3. This solid solution phase behaves as an intermediate and undergoes further reaction with γ-Fe2O3 to give SrFe12O19. No paramagnetic Sr-Fe oxide intermediate is formed. The low temperature of the reactions and the absence of paramagnetic intermediates offer new possibilities for controlling the textures and magnetic properties SrFe12O19 ceramic bodies.

  3. Magnetochemistry of the tetrahaloferrate (III) ions. 7. Crystal structure and magnetic ordering in (pyridinium){sub 3}Fe{sub 2}Br{sub 9}

    SciTech Connect

    Lowe, C.B.; Shaviv, R.; Carlin, R.L.

    1994-07-06

    A monoclinic crystal structure was found by X-ray diffraction for bis [pyridinium tetrabromferrate(III)]-pyridinium bromide. The double salt contains two slightly distorted [FeBr{sub 4}]{sup -} tetrahedra, three pyridinium rings, and an uncoordinated halide in each asymmetric unit, as is characteristic of the A{sub 3}Fe{sub 2}X{sub 9} series of compounds. Unit cell parameters, monoclinic space group P2{sub 1}, are a = 7.656(3) {angstrom}, b = 14.237(5) {angstrom}, c = 13.725(5) {angstrom}, {beta} = 93.42(3){degrees}, and V = 1493(1) {angstrom}{sup 3}, using Mo K{alpha} radiation {lambda} = 0.710 69 {angstrom}, {rho}{sub calc} = 2.38 g cm{sup -3}, and Z = 2. The tetrahedra are aligned with their 3-fold axes parallel to the crystallographic c axis. Bond lengths (Fe-Br) range from 2.271(9) {angstrom} to 2.379(9) {angstrom} for the two different slightly distorted tetrahedral units. Magnetic susceptibility studies show that the material orders three-dimensionally at 7.4 {+-} 0.2 K. The data are compared to a HTS expansion of 1/{sub {chi}} for the S = 5/2 three-dimensional Heisenberg model antiferromagnet for a sc lattice with g = 1.98 and J/k{sub B} = -0.43 K. The specific heat measurements indicate two odd-shaped {lambda} features, at 7.3 and 8 K.

  4. Heterobridged dinuclear, tetranuclear, dinuclear-based 1-d, and heptanuclear-based 1-D complexes of copper(II) derived from a dinucleating ligand: syntheses, structures, magnetochemistry, spectroscopy, and catecholase activity.

    PubMed

    Majumder, Samit; Sarkar, Sohini; Sasmal, Sujit; Sañudo, E Carolina; Mohanta, Sasankasekhar

    2011-08-15

    The work in this paper presents syntheses, characterization, crystal structures, variable-temperature/field magnetic properties, catecholase activity, and electrospray ionization mass spectroscopic (ESI-MS positive) study of five copper(II) complexes of composition [Cu(II)(2)L(μ(1,1)-NO(3))(H(2)O)(NO(3))](NO(3)) (1), [{Cu(II)(2)L(μ-OH)(H(2)O)}(μ-ClO(4))](n)(ClO(4))(n) (2), [{Cu(II)(2)L(NCS)(2)}(μ(1,3)-NCS)](n) (3), [{Cu(II)(2)L(μ(1,1)-N(3))(ClO(4))}(2)(μ(1,3)-N(3))(2)] (4), and [{Cu(II)(2)L(μ-OH)}{Cu(II)(2)L(μ(1,1)-N(3))}{Cu(II)(μ(1,1)-N(3))(4)(dmf)}{Cu(II)(2)(μ(1,1)-N(3))(2)(N(3))(4)}](n)·ndmf (5), derived from a new compartmental ligand 2,6-bis[N-(2-pyridylethyl)formidoyl]-4-ethylphenol, which is the 1:2 condensation product of 4-ethyl-2,6-diformylphenol and 2-(2-aminoethyl)pyridine. The title compounds are either of the following nuclearities/topologies: dinuclear (1), dinuclear-based one-dimensional (2 and 3), tetranuclear (4), and heptanuclear-based one-dimensional (5). The bridging moieties in 1-5 are as follows: μ-phenoxo-μ(1,1)-nitrate (1), μ-phenoxo-μ-hydroxo and μ-perchlorate (2), μ-phenoxo and μ(1,3)-thiocyanate (3), μ-phenoxo-μ(1,1)-azide and μ(1,3)-azide (4), μ-phenoxo-μ-hydroxo, μ-phenoxo-μ(1,1)-azide, and μ(1,1)-azide (5). All the five compounds exhibit overall antiferromagnetic interaction. The J values in 1-4 have been determined (-135 cm(-1) for 1, -298 cm(-1) for 2, -105 cm(-1) for 3, -119.5 cm(-1) for 4). The pairwise interactions in 5 have been evaluated qualitatively to result in S(T) = 3/2 spin ground state, which has been verified by magnetization experiment. Utilizing 3,5-di-tert-butyl catechol (3,5-DTBCH(2)) as the substrate, catecholase activity of all the five complexes have been checked. While 1 and 3 are inactive, complexes 2, 4, and 5 show catecholase activity with turn over numbers 39 h(-1) (for 2), 40 h(-1) (for 4), and 48 h(-1) (for 5) in dmf and 167 h(-1) (for 2) and 215 h(-1) (for 4) in acetonitrile. Conductance of the dmf solution of the complexes has been measured, revealing that bridging moieties and nuclearity have been almost retained in solution. Electrospray ionization mass (ESI-MS positive) spectra of complexes 1, 2, and 4 have been recorded in acetonitrile solutions and the positive ions have been well characterized. ESI-MS positive spectrum of complex 2 in presence of 3,5-DTBCH(2) have also been recorded and, interestingly, a positive ion [Cu(II)(2)L(μ-3,5-DTBC(2-))(3,5-DTBCH(-))Na(I)](+) has been identified. PMID:21776948

  5. Combined analysis of chemical bonding in a Cu(II) dimer using QTAIM, Voronoi tessellation and Hirshfeld surface approaches.

    PubMed

    Vologzhanina, Anna V; Kats, Svitlana V; Penkova, Larisa V; Pavlenko, Vadim A; Efimov, Nikolay N; Minin, Vadim V; Eremenko, Igor L

    2015-10-01

    Interaction of 1-(1H-pyrazol-5-yl)ethanone oxime (H2PzOx) with copper(II) chloride in the presence of pyridine afforded a binuclear discrete [Cu2(HPzOx)2Cl2py2] complex, which was characterized by Fourier transform-IR and electron paramagnetic resonance (EPR) spectra, magnetochemistry and high-resolution X-ray diffraction experiments. Multipole refinement of X-ray diffraction data and density-functional theory (DFT) calculations of an isolated molecule allowed charge and spin distributions to be obtained for this compound. Magnetochemistry data, EPR spectra and DFT calculations of an isolated molecule show antiferromagnetic coupling between copper(II) ions. The spin distribution suggests an exchange pathway via the bridging pyrazole ring in the equatorial plane of the CuN4Cl coordination polyhedron, thus providing support for the classical superexchange mechanism; the calculated value of the magnetic coupling constant -2J is equal to 220 cm(-1), which compares well with the experimental value of 203 ± 2 cm(-1). Chemical connectivity was derived by Bader's 'quantum theory of atoms in molecules' and compared with Voronoi tessellation and Hirshfeld surface representations of crystal space. All methodologies gave a similar qualitative and semi-quantitative description of intra- and intermolecular connectivity. PMID:26428404

  6. Annual Conference on Magnetism and Magnetic Materials, 29th, Pittsburgh, PA, November 8-11, 1983, Proceedings

    SciTech Connect

    Hasegawa, R.; Koon, N.C.; Cooper, B.R.

    1984-03-15

    Various topics on magnetism and magnetic materials are addressed. The subjects considered include: spin glasses, amorphous magnetism, actinide and rare earth intermetallics, magnetic excitation, itinerant magnetism and magnetic structure, valence instabilities, Kondo effect, transport and Hall effects, mixed valence and Kondo compounds, superconductivity and magnetism, d and f electron magnetism and superconductivity, Fe-based microcrystalline and permanent magnetic alloys, hard and soft magnetic materials, and magnetooptics. Also discussed are: numerical methods for magnetic field computation, recording theory and experiments, recording heads and media, magnetic studies via hyperfine interactions, magnetic semiconductors, magnet insulators, transition metal systems, random fields, critical phenomena and magnetoelastic effects and resonance, surfaces and interfaces, magnetostatic waves and resonance, bubble materials and implantation, bubble devices and physics, magnetic separation, ferrofluids, magnetochemistry, new techniques and materials, and new applications.

  7. Magnetic behaviour of layered Ag(II) fluorides.

    PubMed

    McLain, Sylvia E; Dolgos, Michelle R; Tennant, D Alan; Turner, John F C; Barnes, Ted; Proffen, Thomas; Sales, Brian C; Bewley, Robert I

    2006-07-01

    Fluoride phases that contain the spin-1/2 4d9 Ag(II) ion have recently been predicted to have interesting or unusual magnetochemistry, owing to their structural similarity to the 3d9 Cu(II) cuprates and the covalence associated with this unusual oxidation state of silver. Here we present a comprehensive study of structure and magnetism in the layered Ag(II) fluoride Cs2AgF4, using magnetic susceptometry, inelastic neutron scattering techniques and both X-ray and neutron powder diffraction. We find that this material is well described as a two-dimensional ferromagnet, in sharp contrast to the high-T(C) cuprates and a previous report in the literature. Analyses of the structural data show that Cs2AgF4 is orbitally ordered at all temperatures of measurement. Therefore, we suggest that orbital ordering may be the origin of the ferromagnetism we observe in this material. PMID:16783361

  8. Synthesis, characterization, hydrolase and catecholase activity of a dinuclear iron(III) complex: Catalytic promiscuity.

    PubMed

    Camargo, Tiago P; Maia, Fernanda F; Chaves, Cláudia; de Souza, Bernardo; Bortoluzzi, Adailton J; Castilho, Nathalia; Bortolotto, Tiago; Terenzi, Hernán; Castellano, Eduardo E; Haase, Wolfgang; Tomkowicz, Zbigniew; Peralta, Rosely A; Neves, Ademir

    2015-05-01

    Herein, we report the synthesis and characterization of the new di-iron(III) complex [(bbpmp)(H2O)(Cl)Fe(III)(μ-Ophenoxo)Fe(III)(H2O)Cl)]Cl (1), with the symmetrical ligand 2,6-bis{[(2-hydroxybenzyl)(pyridin-2-yl)methylamino]methyl}-4-methylphenol (H3bbpmp). Complexes 2 with the unsymmetrical ligand H2bpbpmp - {2-[[(2-hydroxybenzyl)(2-pyridylmethyl)]aminomethyl]-6-bis(pyridylmethyl) aminomethyl}-4-methylphenol and 3 with the ligand L(1)=4,11-dimethyl-1,8-bis{2-[N-(di-2-pyridylmethyl)amino]ethyl}cyclam were included for comparison purposes. Complex 1 was characterized through elemental analysis, X-ray crystallography, magnetochemistry, electronic spectroscopy, electrochemistry, mass spectrometry and potentiometric titration. The magnetic data show a very weak antiferromagnetic coupling between the two iron centers of the dinuclear complex 1 (J=-0.29cm(-1)). Due to the presence of labile coordination sites in both iron centers the hydrolysis of both the diester model substrate 2,4-BDNPP and DNA was studied in detail. Complex 1 was also able to catalyze the oxidation of the substrate 3,5-di-tert-butylcatechol (3,5-DTBC) to give the corresponding quinone, and thus it can be considered as a catalytically promiscuous system. PMID:25792035

  9. Copper(II) complexes with heterocyclic hydroxyimino-containing ligands

    SciTech Connect

    Kogan, V.A.; Burlov, A.S.; Popov, L.D.; Lukov, V.V.; Koshchienko, Yu.V.; Tsupak, E.B.; Barchan, G.P.; Chigarenko, G.G.; Bolotnikov, V.S.

    1988-05-01

    The reaction of oximes (R = Ph (L'), C=N (L'')) with the copper(II) salts CuA/sub 2/ in methanol has given the complexes CuL/sub 2/ ' x H/sub 2/O and CuL/sub 2//sup ''/ x 2H/sub 2/O (I) (A = Acet/sup -/), CuHLCl/sub 2/ x H/sub 2/O (II) (A = Cl/sup -/), CuLOH(ClO/sub 4/)/sub 2/ x 2H/sub 2/O (III) (A = ClO/sub 4//sup -/) and the complexes Cu/sub 3/L/sub 3//sup '/OH(NO/sub 3/)/sub 2/ and Cu/sub 3/L/sub 3//sup ''/(OH)/sub 2/NO/sub 3/ (IV) (A = NO/sub 3//sup -/). Their physicochemical properties have been studied by the methods of IR spectroscopy and magnetochemistry. It has been shown that complexes I have a chelate structure and that their magnetic moments are not dependent on the temperature. An anti-ferromagnetic exchange interaction takes place in complexes II-IV. On the basis of magnetochemical measurements over a broad temperature range and data calculated in the framework of the Heisenberg-Dirac-Van Vleck model of isotropic exchange interactions, a dimeric structure has been proposed for the complexes of type II, and a trinuclear cluster structure has been proposed for complexes III and IV.

  10. Oxidative Addition of Carbon–Carbon Bonds with a Redox-Active Bis(imino)pyridine Iron Complex

    PubMed Central

    Darmon, Jonathan M.; Stieber, S. Chantal E.; Sylvester, Kevin T.; Fernández, Ignacio; Lobkovsky, Emil; Semproni, Scott P.; Bill, Eckhard; Wieghardt, Karl; DeBeer, Serena; Chirik, Paul J.

    2013-01-01

    Addition of biphenylene to the bis(imino)pyridine iron dinitrogen complexes, (iPrPDI)Fe(N2)2 and [(MePDI)Fe(N2)]2(μ2-N2) (RPDI = 2,6-(2,6-R2—C6H3— N=CMe)2C5H3N; R = Me, iPr), resulted in oxidative addition of a C—C bond at ambient temperature to yield the corresponding iron biphenyl compounds, (RPDI)Fe-(biphenyl). The molecular structures of the resulting bis-(imino)pyridine iron metallacycles were established by X-ray diffraction and revealed idealized square pyramidal geometries. The electronic structures of the compounds were studied by Mössbauer spectroscopy, NMR spectroscopy, magnetochemistry, and X-ray absorption and X-ray emission spectroscopies. The experimental data, in combination with broken-symmetry density functional theory calculations, established spin crossover (low to intermediate spin) ferric compounds antiferromagnetically coupled to bis(imino)pyridine radical anions. Thus, the overall oxidation reaction involves cooperative electron loss from both the iron center and the redox-active bis(imino)pyridine ligand. PMID:23043331

  11. Multidimensional crystal frameworks based on heteropoly blue building block of [SiW10Mo(V)2O40]6-: synthesis, structures and magnetic properties.

    PubMed

    Wang, Yuchao; Li, Fengyan; Xu, Lin; Jiang, Ning; Liu, Xizheng

    2013-04-28

    Four heteropoly blue complexes constructed from Keggin-type heteropoly blue molybdenum-tungsten clusters and Cu(II) ions as linkers, H2[α-SiW10Mo(V)2O40][Cu(PDA)2·H2O]2 (1), H2[α-SiW10Mo(V)2O40][Cu(DEF)3·H2O][Cu(DEF)2·2H2O]·6H2O (2), H2[α-SiW10Mo(V)2O40][Cu(DMF)3H2O]2·6H2O (3), and H4[α-SiW10Mo(V)2O40]2[CuK2(DMF)6][Na0.75K3.25(DMF)6] (4) [PDA = propanediamide, DEF = N,N-diethylformamide and DMF = N,N-dimethylformamide], have been synthesized by conventional reactions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetry, X-ray powder diffraction (XRD) and UV spectra. The amount of Cu(II) and the nature of the ligand (DMF, DEF and PDA) can control both the linkage pattern of Cu(II) ions and the dimensionality of the frameworks; this demonstrates for the first time the possibility to assemble heteropoly blue architectures in different dimensionality ranging from zero-dimensional (0D) to one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D). The magnetic investigation showed that the positive magnetic moment could be observed at room temperature, which should be unusual results in magnetochemistry of the two-electron reduced heteropoly blue. The stability and formation conditions of the four compounds are also discussed. PMID:23455029

  12. Dinuclear palladium complexes with two ligand-centered radicals and a single bridging ligand: subtle tuning of magnetic properties.

    PubMed

    Broere, Daniël L J; Demeshko, Serhiy; de Bruin, Bas; Pidko, Evgeny A; Reek, Joost N H; Siegler, Maxime A; Lutz, Martin; van der Vlugt, Jarl Ivar

    2015-04-01

    The facile and tunable preparation of unique dinuclear [(L(⋅))Pd-X-Pd(L(⋅))] complexes (X = Cl or N3), bearing a ligand radical on each Pd, is disclosed, as well as their magnetochemistry in solution and solid state is reported. Chloride abstraction from [PdCl(NNO(ISQ))] (NNO(ISQ) = iminosemiquinonato) with TlPF6 results in an unusual monochlorido-bridged dinuclear open-shell diradical species, [{Pd(NNO(ISQ))}2(μ-Cl)](+), with an unusually small Pd-Cl-Pd angle (ca. 93°, determined by X-ray). This suggests an intramolecular d(8)-d(8) interaction, which is supported by DFT calculations. SQUID measurements indicate moderate antiferromagnetic spin exchange between the two ligand radicals and an overall singlet ground state in the solid state. VT EPR spectroscopy shows a transient signal corresponding to a triplet state between 20 and 60 K. Complex 2 reacts with PPh3 to generate [Pd(NNO(ISQ))(PPh3)](+) and one equivalent of [PdCl(NNO(ISQ))]. Reacting an 1:1 mixture of [PdCl(NNO(ISQ))] and [Pd(N3)(NNO(ISQ))] furnishes the 1,1-azido-bridged dinuclear diradical [{Pd(NNO(ISQ))}2(κ(1)-N;μ-N3](+), with a Pd-N-Pd angle close to 127° (X-ray). Magnetic and EPR measurements indicate two independent S = 1/2 spin carriers and no magnetic interaction in the solid state. The two diradical species both show no spin exchange in solution, likely because of unhindered rotation around the Pd-X-Pd core. This work demonstrates that a single bridging atom can induce subtle and tunable changes in structural and magnetic properties of novel dinuclear Pd complexes featuring two ligand-based radicals. PMID:25735905

  13. Synthesis, structural characterization and thermal properties of a new copper(II) one-dimensional coordination polymer based on bridging N,N'-bis(2-hydroxybenzylidene)-2,2-dimethylpropane-1,3-diamine and dicyanamide ligands.

    PubMed

    Hopa, Cigdem; Cokay, Ismail

    2016-02-01

    The design and synthesis of polymeric coordination compounds of 3d transition metals are of great interest in the search for functional materials. The coordination chemistry of the copper(II) ion is of interest currently due to potential applications in the areas of molecular biology and magnetochemistry. A novel coordination polymer of Cu(II) with bridging N,N'-bis(2-hydroxyphenyl)-2,2-dimethylpropane-1,3-diamine (H2L-DM) and dicyanamide (dca) ligands, catena-poly[[[μ2-2,2-dimethyl-N,N'-bis(2-oxidobenzylidene)propane-1,3-diamine-1:2κ(6)O,N,N',O':O,O']dicopper(II)]-di-μ-dicyanamido-1:2'κ(2)N(1):N(5);2:1'κ(2)N(1):N(5)], [Cu2(C19H20N2O2)(C2N3)2]n, has been synthesized and characterized by CHN elemental analysis, IR spectroscopy, thermal analysis and X-ray single-crystal diffraction analysis. Structural studies show that the Cu(II) centres in the dimeric asymmetric unit adopt distorted square-pyramidal geometries, as confirmed by the Addison parameter (τ) values. The chelating characteristics of the L-DM(2-) ligand results in the formation of a Cu(II) dimer with a double phenolate bridge in the asymmetric unit. In the crystal, the dimeric units are further linked to adjacent dimeric units through μ1,5-dca bridges to produce one-dimensional polymeric chains. PMID:26846501

  14. High spin d5 complexes of tris(6-hydroxymethyl-2-pyridylmethyl)amine (H3L): hepta-coordinated [Mn(H3L)]Cl2 and linear trinuclear [Fe3L2](ClO4)3.

    PubMed

    Guisado-Barrios, Gregorio; Li, Yang; Slawin, Alexandra M Z; Richens, David T; Gass, Ian A; Murray, Paul R; Yellowlees, Lesley J; Brechin, Euan K

    2008-01-28

    Reaction of MnCl(2).4H(2)O with H(3)L (H(3)L = tris(6-hydroxymethyl-2-pyridylmethyl)amine) in methanol gives hepta-coordinated [Mn(H(3)L)]Cl(2) involving attachment of Mn(II) to all four nitrogens and three hydroxymethyl arms. Reaction of H(3)L with Fe(ClO(4))(2).6H(2)O in CH(3)CN in the presence of NaO(2)CC(6)H(5) in an attempt to make [Fe(III)OH(H(3)L)(O(2)CC(6)H(5))](ClO(4)), a putative model for soybean lipoxygenase-1, instead gave rise to the linear triiron(III) complex [Fe(3)L(2)](ClO(4))(3) with all three hydroxymethyl arms deprotonated and forming three alkoxide bridges between each Fe(III) centre. The central Fe(III) is hexa-coordinated to only the alkoxide bridges and flanked by two hepta-coordinated iron(III) centres analogous to the Mn(ii) complex. [Fe(3)L(2)](ClO(4))(3) exhibits two reversible 1e(-) reductions to mixed-valence [Fe(3)L(2)](2+) and [Fe(3)L(2)](+) forms. Structure data and magnetochemistry on [Fe(3)L(2)](ClO(4))(3) reveals the tightest Fe-O-Fe angle (87.4 degrees ) and shortest Fe...Fe distance (2.834 A) yet found for any weakly antiferromagnetically-coupled high spin alkoxide-bridged di- or triiron(iii) system and challenges current theories involved in correlating the extent/nature of magnetic interactions in such systems based on Fe-O(bridge) distances and Fe-O-Fe angles. The central hexa-alkoxide coordinated Fe(III) is novel and shows a remarkable resistance towards reduction to Fe(II). PMID:18185873

  15. A new family of 1D, 2D and 3D frameworks aggregated from Ni5, Ni4 and Ni7 building units: synthesis, structure, and magnetism.

    PubMed

    Liu, Ya-Hui; Lu, Li-Ping; Zhu, Miao-Li; Feng, Si-Si; Su, Feng

    2016-05-31

    Three new Ni(ii)-clusters based on a Y-shaped ligand (biphenyl-3,4',5-tricarboxylate, H3BPT), [Ni5(HBPT)4(OH)2(H2O)12]n (), [Ni4(BPT)2(OH)2(H2O)6]n·4nH2O (), and [Ni7(BPT)2(1,4-bib)2(OH)6(HCO2)2]n·3nH2O () (1,4-bib = 1,4-bi(1H-imidazol-1-yl)benzene), have been synthesized under solvothermal conditions. They were studied by infrared spectroscopy (IR), single crystal X-ray diffraction, thermogravimetric analysis (TGA), and magnetochemistry. The complexes contain low nuclear Ni-clusters as building units (BUs). Structurally, in , the cluster BUs of [Ni5(μ3-OH)2](8+) can be viewed as two reverse triangles sharing a common vertex, which are connected by the partially deprotonated μ2-η(1):η(1)-HBPT(2-) forming 1D chains. The BUs of [Ni4(μ3-OH)2](6+) clusters in can be considered as two reverse triangles sharing a common edge and extended by deprotonated μ6-η(1):η(1):η(1):η(1):η(2)-BPT(3-) constructing a 2D framework. The 3D framework of complex consists of a [Ni7(μ3-OH)4(R-COO)7(HCO2)3] cluster BUs with fully deprotonated μ5-η(1):η(1):η(1):η(1):η(1):η(1)-BPT(3-) and 1,4-bib ligands. In addition, TGA reveals that the complexes are stable in the range of 293-548 K. Magnetostructural analyses indicate ferromagnetic coupling of J1 = 1.85(3) and J2 = 2.25(4) cm(-1) in and J = 5.76(6) cm(-1) in , whereas magnetic parameters J1 = -2.64(3), J2 = -23.22(19) and J3 = 12.02(5) cm(-1) indicate an alternating magnetic chain (AF/F) in . PMID:27180871

  16. A novel asymmetric di-Ni(II) system as a highly efficient functional model for phosphodiesterase: synthesis, structures, physicochemical properties and catalytic kinetics.

    PubMed

    Ren, Yan-wei; Lu, Jia-xian; Cai, Bo-wei; Shi, Da-bin; Jiang, Huan-feng; Chen, Jun; Zheng, De; Liu, Bin

    2011-02-14

    A novel asymmetric phenol-based 'end-off' dinucleating ligand 2-{[(2-piperidylmethyl)amino]methyl}-4-bromo-6-[(1-methylhomopiperazine-4-yl)methyl]phenol (HL) and three dinuclear nickel(II) complexes, [Ni₂L(μ-OH)] (ClO₄)₂ (1), [Ni₂L(DNBA)₂(CH₃CN)₂]BPh₄ (2) and [Ni₂L(BPP)₂(CH₃CN)₂]BPh₄ (3) have been synthesized and characterized by a variety of techniques including: NMR, infrared and UV-vis spectroscopies, mass spectrometry, elemental analysis, molar conductivity, thermal analysis, magnetochemistry and single-crystal X-ray diffractometry. The UV-vis spectrum of complex 1 exhibits a strong peak at 510 nm, a characteristic absorption of a d-d transition of the square-planar four-coordinated Ni(II) center. Utilizing this feature, the stepwise formation of mono- and dinickel centers in solution can be monitored. Phosphodiesterase activity of a dinuclear Ni(II) system (complex 1), formed in situ by a 2 : 1 mixture of Ni(2+) ions and the ligand HL, was investigated using bis(4-nitrophenyl)phosphate (BNPP) as the substrate. The pH dependence of the BNPP cleavage in water-ethanol (1 : 1, v/v) reveals a bell-shaped pH-k(obs) profile with an optimum at about pH 8.3 which is parallel to the formation of the dinuclear species [Ni₂L(μ-OH)](2+), according to the increase of the peak at 510 nm in the UV-vis absorption spectrum . These studies reveal that the di-Ni(II) system shows the highest catalytic activity reported so far, with an acceleration rate 1.28 × 10⁷ times faster than the uncatalyzed reaction. The bridging hydroxyl group in [Ni₂L(μ-OH)](2+) is responsible for the hydrolysis reaction. The possible mechanism for the BNPP cleavage promoted by di-Ni(II) system is proposed on the basis of kinetic and spectral analyses. This study provides a less common example of the asymmetric phosphodiesterase model, which is like the active sites of most native metallohydrolases. PMID:21180701

  17. Monomeric, trimeric, and tetrameric transition metal complexes (Mn, Fe, Co) containing N,N-bis(2-pyridylmethyl)-2-aminoethanol/-ate: preparation, crystal structure, molecular magnetism and oxidation catalysis.

    PubMed

    Shin, Jong Won; Rowthu, Sankara Rao; Hyun, Min Young; Song, Young Joo; Kim, Cheal; Kim, Bong Gon; Min, Kil Sik

    2011-06-01

    The reaction of N,N-bis(2-pyridylmethyl)-2-aminoethanol (bpaeOH), NaSCN/NaN(3), and metal (M) ions [M = Mn(II), Fe(II/III), Co(II)] in MeOH, leads to the isolation of a series of monomeric, trimeric, and tetrameric metal complexes, namely [Mn(bpaeOH)(NCS)(2)] (1), [Mn(bpaeO)(N(3))(2)] (2), [Fe(bpaeOH)(NCS)(2)] (3), [Fe(4)(bpaeO)(2)(CH(3)O)(2)(N(3))(8)] (4), [Co(bpaeOH)(NCS)(2)] (5), and [Co(3)(bpaeO)(2)(NO(3))(N(3))(4)](NO(3)) (6). These compounds have been investigated by single crystal X-ray diffractometry and magnetochemistry. In complex 1 the Mn(II) is bonded to one bpaeOH and two thiocyanate ions, while in complex 2 it is coordinated to a deprotonated bpaeO(-) and two azide ions. The oxidation states of manganese ions are 2+ for 1 and 3+ for 2, respectively, indicating that the different oxidation states depend on the type of binding anions. The structures of monomeric iron(II) and cobalt(II) complexes 3 and 5 with two thiocyanate ions are isomorphous to that of 1. Compounds 1, 2, 3, and 5 exhibit high-spin states in the temperature range 5 to 300 K. 4 contains two different iron(III) ions in an asymmetric unit, one is coordinated to a deprotonated bpaeO(-), an azide ion, and a methoxy group, and the other is bonded to three azide ions and two oxygens from bpaeO(-) and a methoxy group. Two independent iron(III) ions in 4 form a tetranuclear complex by symmetry. 4 displays both ferromagnetic and antiferromagnetic couplings (J = 9.8 and -14.3 cm(-1)) between the iron(III) ions. 6 is a mixed-valence trinuclear cobalt complex, which is formulated as Co(III)(S = 0)-Co(II)(S = 3/2)-Co(III)(S = 0). The effective magnetic moment at room temperature corresponds to the high-spin cobalt(II) ion (∼4.27 μ(B)). Interestingly, 6 showed efficient catalytic activities toward various olefins and alcohols with modest to excellent yields, and it has been proposed that a high-valent Co(V)-oxo species might be responsible for oxygen atom transfer in the olefin epoxidation and

  18. Dicopper(II) metallacyclophanes as multifunctional magnetic devices: a joint experimental and computational study.

    PubMed

    Castellano, María; Ruiz-García, Rafael; Cano, Joan; Ferrando-Soria, Jesús; Pardo, Emilio; Fortea-Pérez, Francisco R; Stiriba, Salah-Eddine; Julve, Miguel; Lloret, Francesc

    2015-03-17

    Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocalization through a molecular assembly in response to one or many input signals leads to the concept of developing a molecule-based spintronics that can be viewed as a potential alternative to the classical molecule-based electronics. A great variety of factors can influence over these electronically or magnetically coupled, metallosupramolecular complexes in a reversible manner, electronic or photonic external stimuli being the most promising ones. The response ability of the metal centers and/or the organic bridging ligands to the application of an electric field or light irradiation, together with the geometrical features that allow the precise positioning in space of substituent groups, make these metal-organic systems particularly suitable to build highly integrated molecular spintronic circuits. In this Account, we describe the chemistry and physics of dinuclear copper(II) metallacyclophanes with oxamato-containing dinucleating ligands featuring redox- and photoactive aromatic spacers. Our recent works on dicopper(II) metallacyclophanes and earlier ones on related organic cyclophanes are now compared in a critical manner. Special focus is placed on the ligand design as well as in the combination of experimental and computational methods to demonstrate the multifunctionality