Hydrothermal synthesis, structure characterization of a new mixed Mo/V metal-oxygen cluster compound: [Co(phen)(3)](2)[HPMo4V (Mo4V6IV)-V-VI M2O44]center dot 4H(2)O, (M=0.78Mo(V)+0.22V(IV))

A new polyoxometalate [Co(phen)(3)](2)[HPMo4V Mo-4(VI) V-6(IV) M2O44]center dot 4H(2)O (M = 0.78Mo(V)+ 0.22V(IV)) 1 was hydrothermally synthesized and characterized by IR, elemental analyses, X-ray photoelectron spectrum, ESR and single crystal X-ray diffraction. The title compound is in the triclinic space group P (1) over bar with a = 12.0953(7) angstrom, b = 14.0182(6) angstrom, c = 14.6468(7) angstrom, V=2402.55(18) angstrom(3), alpha = 105.134(2), beta = 91.841(3), gamma = 91.401(2), Z = 1, and R-1 (wR(2)) = 0.0617 (0.1701). The compound was prepared from tetra-capped pseudo-Kepin with phosphorus-centered polyoxoanions [PMo8V6M2O44](5-) , [Co(phen)(3)](2+) cations and linked through hydrogen bonds and pi-pi stacking interaction into three-dimensional supramolecular framework. Astudy of the magnetic properties of 1 demonstrates that it exhibits antiferromagnetic coupling interactions.

High-dimensional assembly depending on polyoxoanion templates, metal ion coordination geometries, and a flexible bis(imidazole) ligand

By introducing the flexible 1,1'-(1,4-butanediyl)bis(imidazole) (bbi) ligand into the polyoxovanadate system, five novel polyoxoanion-templated architectures based on [As8V14O42](4-) and [V16O38Cl](6-) building blocks were obtained: [M(bbi)(2)](2)[As8V14O42(H2O)] [M = Co (1), Ni (2), and Zn (3)], [Cu(bbi)](4)[As8V14O42(H2O)] (4), and [Cu(bbi)](6)[V16O38Cl] (5). Compounds 1-3 are isostructural, and they exhibit a binodal (4,6)-connected 2D structure with Schlafli symbol (3(4)center dot 4(2))(3(4)center dot 4(4)center dot 5(4)center dot 6(3))(2), in which the polyoxoanion induces a closed four-membered circuit of M-4(bbi)(4). Compound 4 exhibits an interesting 3D framework constructed from tetradentate [As8V14O42](4-) cluster anions and cationic ladderlike double chains. There exists a bigger M-8(bbi)(6)O-2 circuit in 4. The 3D extended structure of 5 is composed of heptadentate [V16O38Cl](6-) anions and flexural cationic chains; the latter consists of six Cu(bbi) segments arranged alternately. It presents the largest 24-membered circuit of M-24(bbi)(24) so far observed made of bbi molecules and transition-metal cations. Investigation of their structural relations shows the important template role of the polyoxoanions and the synergetic interactions among the polyoxoanions, transition-metal ions, and flexible ligand in the assembly process.

Hydrothermal synthesis and crystal structure of a sulfur-bridged binuclear copper(II) coordination polymer generated by a spontaneous reduction

A simultaneous reduction SO42- to S2- by 2,5-pyridinedicarboxylate under hydrothermal conditions produced a new binuclear copper(II) coordination polymer [CuS(4,4'-bipy)](n) (4,4-bipy = 4,4'-bipyridine) (1). Single crystal X-ray analysis revealed that compound I consisted of sulfur-bridged binuclear copper(II) units with Cu-Cu bonding which were combined with 4,4-bipy to generate a three-dimensional network constructed from mutual interpenetration of two-dimensional (6,3) nets. Crystal data for 1:C10H8CuN2S, tetragonal 14(1)/acd, a = 14.0686(5) Angstrom, b = 14.0686(5) Angstrom, c = 38.759(2) Angstrom, Z = 32. Other characterizations by elemental analysis, IR, EPR and TGA analysis were also described in this paper.

Preparation of Ni0.65Zn0.35Cu0.1Fe1.9O4/SiO2 nanocomposites by sol-gel method

(Ni0.65Zn035Cu0.1Fe1.904)-Cu-./SiO2 natiocomposites were fabricated by the sol-gel method using tetraethylorthosilicate as a precursor of silica, and metal nitrates as precursors of NiZnCu ferrite. With infrared spectra, X-ray diffraction, transmission electron microscope, Raman spectra, Mossbauer spectroscopy and vibrating sample magnetometer measurements, the formation of single phase nanocrystalline NiZnCu ferrites dispersed in silica matrix is confirmed when the sample is annealed at 550degreesC. The transition from the paramagnetic to the ferromagnetic state is observed as the annealing temperature increases from 750degreesC to 1150degreesC. The magnetic properties of these nanocomposites are clearly size dependent. The saturation magnetization increases with the annealing temperature.

Rapid synthesis of Mn0.65Zn0.35Fe2O4/SiO2 homogeneous nanocomposites by modified sol-gel auto-combustion method

MnZn-ferrite/SiO2 nanocomposites with different silica content were successfully fabricated by a novel modified sol-gel auto-combustion method using citric acid as a chelating agent and tetraethyl orthosilicate (TEOS) as the source of silica matrix. The auto-combustion nature of the dried gel was studied by X-ray diffraction (XRD), Infrared spectra (IR), thermogravimetry (TG) and differential thermal analysis (DTA). Transmission electron microscope (TEM) observation shows that the MnZn-ferrite particles are homogeneously dispersed in silica matrix after auto-combustion of the dried gels. The magnetic properties vary with the silica content. The transition from the ferromagnetic to paramagnetic state is observed by Mossbauer spectra measurement with the increasing silica content. Vibrating sample magnetometer (VSM) shows that the magnetic properties of Mn0.65Zn0.35Fe2O4/SiO2 nanocomposites strongly depend on the silica content.

A study of NiZnCu-ferrite/SiO2 nanocomposites with different ferrite contents synthesized by sol-gel method

Ni0.65Zn0.35Cu0.1Fe1.9O4/SiO2 nanocomposites with different weight percentages of NiZnCu-ferrite dispersed in silica matrix were successfully fabricated by the sol-gel method using tetraethylorthosilicate (TEOS) as a precursor of silica, and metal nitrates as precursors of NiZnCu ferrite. The thermal decomposition process of the dried gel was studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The obtained Ni0.65Zn0.35Cu0.1Fe1.9O4/SiO2 nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), Mossbauer spectroscopy and vibrating sample magnetometry (VSM). The formation of stoichiometric NiZnCu-ferrite dispersed in silica matrix is confirmed when the weight percentage of ferrite is not more than 30%. Samples with higher ferrite content have small amount of alpha-Fe2O3. The transition from the paramagnetic to the ferromagnetic state is observed as the ferrite content increases from 20 to 90wt%.

Heptaaquatetra-mu(3)-hydroxy-hexa-mu(2)-L-leucine-(L-leucine)tetraytterbium(III) tetrachlorozinc(II) trichlorohydroxyzinc(II) tetrachloride octahydrate

The title bimetallic compound, [Yb-4(mu(3)-OH)(4)(C6H13NO2)(7)-(H2O)(7)][ZnCl4][ZnCl3(OH)]Cl-4.8H(2)O, was synthesized at near physiological pH (6.0). The compound exhibits some novel structural features, including an asymmetric [Yb-4(mu(3)-OH)(4)(L-leucine)(7)(H2O)(7)](8+) complex cation in which four OH groups act as bridging ligands, linking four Yb3+ cations into a Yb4O4 structural unit. Each pair of adjacent Yb3+ ions is further bridged by one carboxy group from a leucine ligand. Water molecules and a monodentate leucine ligand also coordinate to Yb3+ ions, completing their eight-coordinate square-antiprismatic coordination. The Yb-4(mu(3)-OH)(4)(L-leucine)(7)(H2O)(7)](8+) cation, the [ZnCl4](2-), [ZnCl3OH](2-) and Cl- anions, and the lattice water molecules are linked via hydrogen bonds.

Large-scale synthesis of Berlin green Fe[Fe(CN)(6)] microcubic crystals

Berlin green FeFe(CN)(6) microcubic crystals have been successfully prepared by a simple hydrothermal process between K-3[Fe(CN)(6)] with Na2S2O3 aqueous solution, free of any surfactant or template. The experimental results clearly show that the molar ratio of K-3[Fe(CN)(6)] to Na2S2O3 and their concentrations are the dominant processing factors in controlling the size, morphology, and composition of the resulting products.

Synthesis, structural and electrical characterizations of Sr2Fe1-xMxNbO6 (M = Zn and Cu) with double perovskite structure

Sr2Fe1-xZnxNbO6-x/2 (0 <= x <= 0.5) and Sr2Fe1-xCuxNbO6-x/2 (0.01 <= x <= 0.05) with the double perovskite structure have been synthesized. The crystal structures at room temperature were determined from Rietveld refinements of X-ray powder diffraction data. The plots of the imaginary parts of the impedance spectrum, Z '', and the electric modulus, M '', versus log (frequency), possess maxima for both curves separated by less than a half decade in frequency with associated capacities of 2 nF. The enhancement of the overall conductivity Of Sr2Fe1-xMxNbO6-x/2 (M = Cu and Zn) is observed, as increases from 2.48 (3) x 10(-4) S/cm for Sr2FeNbO6 to 3.82 (5) x 10(-3) S/cm for Sr2Fe0.8Zn0.2NbO5.9 at 673 K. Sr2Fe0.8Zn0.2NbO5.9 is chemically stable under the oxygen partial pressure from 1 atm to 10(-22) atm at 873 K. The p and n-type electronic conductions are dominant under oxidizing and reducing conditions, respectively, suggesting a small-polaron hopping mechanism of electronic conduction.

Synthesis of nanocrystalline Ba(CoxZn1-x)(2)Fe16O27 by sol-gel auto-combustion method

The synthesis of nanocrystalline W-type hexaferrites Ba(CoxZn1-x)(2)Fe16O27 powders by sol-gel auto-combustion method has been investigated. The thermal decomposition process of dried gel was studied by thermogravimetry (TG), differential thermal analysis (DTA) and infrared spectra (IR). The structural and magnetic properties of resultant particles were investigated by X-ray diffraction (XRD), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). The results reveal that the dried gel exhibits auto-combustion behavior. After combustion, pure nanocrystalline W-type hexaferrite phase starts to appear at the calcination temperature of 800 degrees C. The crystallinity and the grain size increase at higher temperature. The saturation magnetization and coercivity clearly depend on calcination temperature and Co content X.

Synthesis, characterization and crystal structure of a new layered heterometallic coordination polymer {[(CuL) Sr-2(H2O)center dot Sr-2(H2O)(7)]center dot 2H(2)O center dot 0.5CH(3)OH}(n)

A copper-strontium heterometallic coordination polymer was synthesized and characterized by elemental analysis and IR spectra. The crystal structure was determined by single-crystal X-ray diffraction analyses. The title complex is a 2 D coordination polymer with the chemical formula [[(CuL)(2)Sr (H2O) center dot Sr-2 ((HO)-O-2)(7)]center dot 2H(2)O center dot 0.5CH(3)OH](n), where H4L = N-(2-hydroxybenzamido)-N'-(3-carboxylsalicylidene) ethylenediamine. Its structural unit is comprised of two adjacent units, which polymerized with each other to form a new layered heterometallic coordination polymer.

Synthesis and structural characterization of a new molecule-based complex constructed from dodecamolybdophosphoric acid and imidazole

A new compound, (CH5N2)(3)(PMo12O40CH4N23H2O)-C-.-H-. (1), was synthesized and structurally characterized by elemental analyses, IR spectra, UV spectra, NMR spectra and ESR spectra. This is, to our knowledge, the first example of an imidazole-polyoxometalate species. The compound was recrystallized from N,N-dimethylformamide (DMF), and then black block-like crystals of (C3H5N2)(4)((PMoMo11O40)-Mo-V-O-VI)(.)4C(3)H(7)NO(.) 2H(2)O (2), were obtained. It crystallizes in a triclinic space group P (1) over bar with n=12.423(3) Angstrom, b=12.666(3) Angstrom, c=13.341(3) Angstrom, alpha=70.56(3)degrees, beta=71.16(3)degrees, gamma=64.18(3)degrees, V= 1742.3(6) Angstrom(3), Z=1, R1 = 0.0585, wR2 = 0.1885. An X-ray crystallographic study showed that the crystal structure is constructed by electrostatic attractions and hydrogen bonds between a dodecamolybdophosphoric anion and an imidazole. The imidazole and DMF molecules occupy cavities in a polyoxometalate lattice ordered along a c-axis. The structure of (2) is similar to that of (1) from a comparison of both IR spectra and TGA Curves.

Heptairon bis(phosphate) tetrakis(hydrogenphosphate)

A new iron hydrogen phosphate, heptairon bis(phosphate) tetrakis(hydrogenphosphate), Fe-7(PO4)(2)(HPO4)(4), has been prepared hydrothermally and characterized by single-crystal X-ray diffraction. The compound has one Fe atom on an inversion centre and is isostructural with Mn-7(PO4)(2)(HPO4)(4) and Co-7(PO4)(2)(HPO4)(4). The structure is based on a framework of edge- and corner-sharing FeO6, Fe-5 and PO4 polyhedra, isotypic with that found in the mixed-valence iron phosphate Fe-7(PO4)(6). The Fe atoms in the title compound are purely in the divalent state, just like the Co atoms in Co-7(PO4)(2)(HPO4)(4), the necessary charge balance being maintained by the addition of H atoms in the form of bridging Fe-OH-P groups.

Hydrothermal synthesis and crystal structure of a hybrid material based on [Co-4(phen)(8)(H2O)(2)(HPO3)(2)](4+) and a highly reduced polyoxoanion

An unusual composite hybrid material [Co-4 (phen)(8) (H2O)(2) (HPO3)(2)](H3O)(3) [PMo8VI V-4(IV) O-40 ((VO)-O-IV) 2] 1 (phen = 1,10-phenanthroline) has been hydrothermally synthesized from a mixture of NH4VO3, Na2MoO4.2H(2)O, CoCl2.6H(2)O, phen, H3PO3 and water. It was characterized by elemental analysis, IR, UV-vis, XPS, EPR, TG and single crystal X-ray diffraction. The title compound is constructed from the organic-inorganic hybrid [Co-4(phen)(8)(H2O)(2) (HPO3)(2)](4+) and highly reduced bi-capped pseudo-Keggin [(PMo8V4O40)-V-VI-O-IV ((VO)-O-IV)(2)](7-) polyoxoanions The structure exhibits an extended 2D network through hydrogen bonds among cations, anions and H2O, combining polyoxometalates with metal phosphonates for the first time.

An organic-inorganic vanadium oxide with one-dimensional ladder-type structure: hydrothermal synthesis, structure and characterization of [V4O10(o-phen)(2)]

A novel organic-inorganic hybrid vanadium oxide [V4O10(o-phen)(2)], involving all vanadium atoms present in +5 oxidation, has been hydrothermally synthesized and characterized by elemental analysis, IR, UV-vis, ESR, XPS spectra and TG-DTA thermal analysis. The single-crystal X-ray diffraction shows that the red-brown crystal is formed in the triclinic system, space group P (1) over bar, a = 9.782(2), b = 6.5124(14), c = 19.765(4) Angstrom, alpha = 89.94(2)degrees, beta = 100.66(2)degrees, gamma = 89.86(2)degrees. The title compound exhibits an infinite one-dimensional ladder-type tetravanadate skeleton with organonitrogen donors of o-phenanthroline ligands coordinated directly to the vanadium oxide framework.