X-ray Crystal Structure and Characterization of Tetra-vanadyl Capped Highly Reduced Polyoxometalate Anion [PMo_5~ⅥMo_7~ⅤO_(40)(V~ⅣO)_4]^(2-)

A novel polyoxometalate [H3O][PMo5^ⅥMo7^ⅤO40 （V^ⅣO）4]·6Py （Py = pyridine） was synthesized and characterized by IR spectrometry, TG and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic space group（C2/m） with α=1.3680（3） nm, b=2.1740（4） nm, c=1.1630（2） nm, β= 118.62（3）°, V= 3. 0362 （10） nm^3, Z = 2, and Rt （wR2） = 0. 0772 （0. 2312）. The compound contains a highly reduced vanadylpoly-molybdophosphate polyoxometalate anion with a four-capped structure. The four {VO} units cap four opposite pits of the pseudo-Keggin core {PMo12O40}.

Kinetics of Photocatalytic Degradation of Formic Acid over Silica Composite Films Based on Polyoxometalates

The composite films, XW11O39n-/SiO2, (X refers to Si, Ge or P, respectively) were prepared by tetraethoxysilane (TEOS) hydrolysis sol-gel method via spin-coating technique. Formation of the composite films is due to strong chemical reaction of organic silanol group with the surface oxygen atoms of XW11O39n-, resulted in the saturation of the surface of the lacunary polyoxometalates (POMs). Therefore, the coordination structural model of the films was proposed. As for the films, retention of the primary Keggin structure was confirmed by UV-vis, FT-IR spectra and MAS NMR. The surface morphology of the films was characterized by SEM, indicating that the film surface is relatively uniform, and the layer thickness is in the range of 250~350 nm. Aqueous formic acid (FA) (0-20 mmol/L) was degraded into CO2 and H2O by irradiating the films in the near-UV area. The results show that all the films have photocatalytic activities and the degradation reaction follows Langmuir-Hinshelwood first order kinetics.

Orientations of Rare-earth-containing Heteropolyoxometalates with Different Sizes in the Interlayer of Synthetic Multibilayer Films

Three rare-earth-containing heteropolyoxometalates with different sizes, Na9[Eu(W5 O18)2], K13[Eu(SiW11O39)2], and K17[Eu(P2W17O61)2], have been incorporated by self-assembly into the interlayer of synthetic multibilayer films of dimethyldioctadecylammonium chloride and exhibited different orientations.

Hydrothermal Synthesis,Crystal Structure and Spectral Characterization of a New Copper Isopolytungstate: [Cu(phen)_3][W_6O_(19)]

An unusual inorganic-organic hybrid hexatungstate complex [Cu（phen）3][W6O19] 1 （C36H24 CuN6O19W6, Mr= 2011.20） was hydrothermally synthesized and characterized by singlecrystal X-ray diffraction, IR spectrum, UV-VIS spectrum and elemental analyses. This compound crystallizes in the monoclinic system, space group C2/c with a = 19.1005（11）, b = 11.2585（11）, c = 20.2867（15） A, β= 102.177（2）°, V= 4264.4 A^ 3, μ（MoKa） = 16.691 mm^-1, Dc = 3.133 g/cm^3, Z = 4, F（000） = 3628, the final R = 0.0338 and wR = 0.0798 for 4090 observed reflections with I 〉 2σ（I）. The result of structure determination shows that the crystal structure is constructed from [W6O19]^2- cluster anions and [Cu（phen）3]^2＋ complex fragments, which are held together into a three-dimensional network through hydrogen-bonding interactions.

Hydrothermal Synthesis and Structure of [CH3NH3]2[(VⅣO)2(VⅤO4)2]:A New Layered Mixed-valence Vanadium Oxide Incorporated with Organic Cations

A new layered mixed valence vanadium oxide, [CH 3NH 3] 2[(V ⅣO) 2(V ⅤO 4) 2], which contains interlamellar organic cations was prepared under hydrothermal conditions and its single crystal structure was determined. It crystallizes in a triclinic system with space group P 1, a =0 625 59(8) nm, b =0 639 84(9) nm, c =0 747 19(10) nm, α =78 718(2)°, β =80 099(2)°, γ =77 100(2). The compound contains mixed valence V 4+ /V 5+ vanadium oxide layers constructed from VO 4 tetrahedra, pairs of edge sharing VO 5 square pyramid and methylamine with protonated organic amines occupying the interlayer space.

Synthesis, Structure Characterization and Biological Activity of Layered Vanadium Oxides [NH_3(CH_2)_2NH(CH_2)_2NH_3][V_6O_(14)]

A new layered vanadium oxide [ NH3 （ CH2 ）2NH（ CH2 ）2NH3 ] [ V6O14 ] （ compound 1 ） was synthesized and characterized by elemental analysis, IR spectrometry and single crystal X ray diffraction. The compound crystallizes ina monoclinic space group P2（1）/n with a = 1.0254（2） nm, b =0.6739（2） nm, c = 1.2400（2） nm, ,8 = 93.88 （ 3 ） °, V = 0. 8549 （ 3 ）nm^3, Z = 2, R1 = 0. 0366, wR2 = 0. 1038. Compound 1 consists of two-dimensional mixed-valence vanadium oxide layers parallelling to the bc plane. The anti-tumor activity of the compound was estimated in three human tumor cell lines in vitro.

Hydrothermal Synthesis, Crystal Structure and Property of a Novel Inorganic-organic Hybrid Compound Based on Phosphomolybdate Anion [H-IDP]_4[PMo_(12)O_(40)]·8H_2O (IDP = 4-(Imidazole-1-yl)phenol)

A novel compound [H-IDP]4[PMo12O40]·8H2O 1 based on Keggin-type phosphor- molybdate has been synthesized by hydrothermal method and characterized by IR spectroscopy, elemental analyses and single-crystal X-ray diffraction. The composite crystallizes in the mono- clinic system, space group C2/m with a = 13.937（5）, b = 27.033（5）, c = 10.857（5） A, β = 122.489（5）°, V = 3450（2）A^3, Mr = 2611.11, Z = 2, Dc = 2.498 g/cm^3, F（000） = 2486,μ = 2.243 mm^-1, the final R = 0.0568 and wR = 0.1216 for 2707 observed reflections with I 〉 2σ（I）. X-ray structural study shows that 1 consists of a [PMo12O40]^4- polyanion, four protonated IDP cations and eight H2O molecules. In the structure of 1, a 3D network forms by hydrogen bond of [PMo12O40]^4- polyanion, HIDP^＋ cation and H2O molecules. Upon excitation wavelength of 280 nrn in hydroxylic solvents at room temperature, 1 shows fluorescence property.

Ce(H_2O)_7Al(OH)_6Mo_6O_(18)·4H_2O: A New One-dimensional Zigzag Chainlike Structure of Anderson Cluster Linked by Cerium Ions

A new cerium polyoxomolybdate { [Ce （ H2 O） 7 Al （ OH ） 6 Mo6 O18 ] · 4H20 } （ compound 1 ） was synthesized and characterized by X-ray diffraction analysis, elemental analysis, TG analysis and IR spectrometry. Compound 1 exhibits a zigzag chain-like structure, which is constructed from an Anderson type anion and rare earth metal, Ce（ Ⅲ ）. These 1-D chains are further extended into a 3-D network by the aid of muhipoint hydrogen-bonding interactions.

Synthesis of Coordination Polymers Using Different Maleic Acid Ligands under Hydrothermal Conditions

A novel coordination polymer, [ Ni （mal） （1,10＇-phen） （ H2O） ] n （ 1 ） （ mal = malate, 1,10＇-phen = 1,10- phenanthroline） was synthesized using malic acid which was generated from maleic acid via hydrothermal reaction. Complex 1, which displays a two-dimensional supramolecular network, was formed by the addition reaction of Ni and maleic acid with water molecules. To our knowledge, several coordination polymers have been directly synthesized from malic acid, but these types of complexes have seldom been synthesized from maleic acid via hydrothermal reactions. When Ni（ Ⅱ ） ion was changed to Zn（ Ⅱ） ion under the same condition, two-dimensional covalent complex 2 [ Zn2 （fma） 2 （1,10＇-phen） 2 ] n （fma = fumatic acid） was formed. Furthermore, complex 2 exhibits intense photolumi- nescent property at room temperature.

Hydrothermal Synthesis and Crystal Structure of a New Supramolecular Channel Framework Based on Cu Complexes and Polyoxovanadate:[Cu(I)(phen)_2]_5[HV_(15)O_(36)(Cl)]_(0.65)[H_3V_(16)O_(38)(Cl)]_(0.35)·2H_2O

A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （tris（hydroxymethyl）aminomethane） and H2O in the molar ratio of 3：1：1：0.5：2.5：1400. Compound 1 crystallizes in the space group P42212 of the tetragonal system with a = b = 21.5009（8）, c = 28.401（2） A, V= 13129.5（12） A^3 Z = 4, Dc = 1.800 g/cm^3, μ（MoKa） = 1.932 mm^-1, λ（MoKa） = 0.71073 A, F（000） = 7063.4, C120H81.20ClCu5N20O38.7V15.35, Mr = 3557.58, the final R = 0.0594 and wR= 0.1320 for 7761 observed reflections （I 〉 2σ（I））. Structure analysis shows that 1 exhibits a 3D channel framework formed by the supramolecular assembly of Cu complexes and polyoxovanadate clusters via intermolecular hydrogen bonding, and the channels contain Cu complexes. Other characterizations by elemental analysis, XPS, IR, XRD and thermal analysis are also described.

Synthesis and Structure of a Novel Chain-like Inorganic-organic Hybrid Constructed from Isopolyanion and Oxalato-bridged Dinuclear Copper Complex

A novel inorganic-organic hybrid based on isopolyanion,{[Cu2（phen）2（μ-ox）][H2Mo8O26]}·4EtOH·Et2O（1） （phen=phenanthroline,ox=oxalate）,was synthesized under open-air mild reaction conditions,and characterized by elemental analysis,IR,ICP,TG and single crystal X-ray diffraction analysis.The crystal structure belongs to triclinic system with space group Pī and cell parameters：a=1.1075（5） nm,b=1.1608（5） nm,c=1.3333（5） nm,α=91.683（5）o,β=113.996（5）o,γ=112.170（5）o,V=1.4159（10） nm3,Mr=2017.44,Z=1,Dc=2.366 g/cm3 and F（000）=980.0.The structure of hybrid 1 is a 1D chain constructed of alternating octamolybdate isopolyanions [β-（Mo8O26）4-] and oxalato-bridged dinuclear copper complex cations [Cu2（phen）2（μ-ox）]2＋.Ultimately,a 3D supramolecular network was formed by hydrogen bond interactions among the adjacent chains.The result shows that hybrid 1 is the first example of inorganic-organic hybrid constructed from isopolyanion and oxalato-bridged dinuclear copper complex fragment （CCDC No.665101）.

A new extended structural compound based on saturated Wells-Dawson polyoxoanions

A new 3D extended structural compound, （dpdo）2H2{[Cu（2,2＇-bipy）212（P2W18O62）}.SH2O 1 （dpdo = 4,4＇-bipyridine-N,N＇- dioxide; 2,2＇-bipy = 2,2＇-bipyridine）, has been hydrothermally synthesized and characterized by elemental analyses, IR, TG analyses, cyclic voltammetry, and single-crystal X-my diffraction. Compound 1 is built up of [P2WlsO62]6- cluster as the structural motif covalently linked by [Cu（2,2＇-bipy）2]^2＋ coordination complexes to yield the 1D chains, which axe further in close contact forming a 3D supramolecular framework via aromatic π-π stacking interactions and extensive hydrogen-bonding interactions among polyoxoanions, coordinated 2,2＇-bipy organic ligands, free dpdo organic molecules and lattice water molecules.

Hydrothermal Synthesis and Properties of Open-Framework Mixed-valence Iron Phosphates IIIII21.543FeFe(PO) with Three-dimensional Structure

The open-framework iron phosphate IIIII21.543FeFe(PO) was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, =104.447(2)? =108.919(4)? =101.741(4)? V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo K?(=0.071073 nm) at 293(2) K in the range of 2.43埃迹?7.46? The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically in-dependent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.

A Novel Three-dimensional Framework with Tunnels Based on the Cobalt-containing Molybdenum Phosphate Moieties

A novel compound (H(2)en)(5) [CoMo12O50P8 (OH)(12)] . 2H(2)O (1) (en = H2NCH2CH2NH2) has been hydrothermally synthesized and characterized by elemental analyses, IR, EPR, XPS spectra and single-crystal X-ray diffraction analyses. Compound 1 crystallizes in a triclinic system, space group P1, with a = 1.1863 (2) nm, b = 1.3361(3) nm, c = 1.3783(3) nm, alpha = 88.13(3)degrees, beta = 70.09(3)degrees, gamma = 65.24(3)degrees, V = 1.8497(6) nm(3), and R = 0.0417. The basic building blocks of compound 1 an {Mo6P4} clusters forming dimers through the {CoO6} octahedra. Compound 1 exhibits an unusual three-dimensional framework with tunnels owing to the extensive hydrogen bonding interactions between the dimers and H(2)en.