Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [CoⅡ(2,2''-bipy)2(H2O)]2[SiWVI12O40]·2H2O

A Keggin-type tungstosilicate compound [CoII(2,2'-bipy)2(H2O)]2[SiWVI12O40]·2H2O1 (bipy = bipyridine) was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C4H40Co2N8O44SiW12) crystallizes in the triclinic system, space group P1 with a = 10.4979(6), b = 13.3946(7), c = 13.5756(8) (A°), α= 70.0769(18), β= 68.910(3), y = 74.186(4)°,V =1649.84(16) (A°)3, M, = 3688.95, Z =1, Dc= 3.713 mg.m-3,μ= 21.432 mm-1, F(000) = 1644, S =1.058, the final R = 0.0511 and wR = 0.1023 for 6523 observed reflections (I> 2σ(I)). Compound 1 consists of two coordinated cation fragments [CoII(2,2'-bipy)2(H2O)]2+, one normal Keggin polyanion unit [SiWVI12O40]4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photo-luminescence property in the solid state at room temperature.     

Hydrothermal Synthesis and Crystal Structure of a Novel Polyoxometalate K(C_4N_2H_(12))_4(C_4N_2H_(11))_(2-)[Mo_8~ⅤMo_4~ⅥCdP_8O_(54)(OH)_8]F·6H_2O

The title compound 1 has been synthesized by the reaction of H_2MoO_4, CdCl_2, H_3PO_4, KF, piperazine hexahydrate and water in aqueous solution under mild hydrothermal conditions. Single-crystal X-ray analysis reveals that the title compound crystallizes in the triclinic system, space group P(-1) with a = 14.049(3), b = 15.972(3), c = 20.043(4) (A), α = 85.82(3), β = 81.28(3),γ = 67.15(3)°, V= 4095.9(14) (A)~3, M_r = 3204.62, Z=2,D_c = 2.598 g/cm~3,μ = 2.360 mm~(-1), F(000) = 3124, the final R = 0.0314, wR = 0.0826 and S = 0.989 for 18592 observed reflections with I > 2σ(I). The crystal packing is stabilized by N-H…O and O-H…O intra- and intermolecular hydrogen bonds to form an infinite 3D network.     

Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O

A Keggin-type tungstosilicate compound [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O 1 （bipy = bipyridine） was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 （C40H40Co2N8O44SiW12） crystallizes in the triclinic system, space group P1 with a = 10.4979（6）, b = 13.3946（7）, c = 13.5756（8）A, α= 70.0769（18）, β = 68.910（3）, γ = 74.186（4）°, V = 1649.84（16）A^3, Mr = 3688.95, Z = 1, Dc = 3.713 mg·m^-3, μ = 21.432 mm^-1, F（000） = 1644, S = 1.058, the final R = 0.0511 and wR =0.1023 for 6523 observed reflections （I 〉 2σ（I））. Compound 1 consists of two coordinated cation fragments [Co^Ⅱ（2,2′-bipy）2（H2O）]^2＋, one normal Keggin polyanion unit [SiW^Ⅵ12O40]^4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photoluminescence property in the solid state at room temperature.     

Synthesis, crystal structure and catalytic activity of a Waugh type polyoxometalate H12[MnMo9O32(KO)6]

A Waugh type polyoxometalate H₁₂[MnMo₉O₃₂(KO)₆] has been synthesized and characterized by single crystal X-ray diffraction, IR, XRD and TG. The compound was crystallized in the trigonal system, space group R3 with a = 15.5380(6) nm, b = 15.5380(6) nm, c = 12.3777(5) nm, α = 90°, β = 90°, γ = 120°, V = 2587.98(18) nm³, Z = 3, R ₁ = 0.0134, θR ₂ = 0.0308. The catalytic activity of the title compound for the dehydration of cyclohexanol was determined. The conversion of C₆H₁₁OH reached 69.56% and the selectivity of C₆H₁₀ was 96% when the amount of catalyst, temperature range and reaction time were 6.59%, 170°C–180°C, 30 min, respectively. Translated from Chinese Journal of Applied Chemistry, 2006, 23(9): 1000–1005 (in Chinese)     

A Novel Composite Based On Phosphotungstate Anion[n-Bu4N][Cu(2,2-bipy)3][PW12O40]·CH3CN·H2O

A novel composite, [C16H36N][Cu(2,2-bipy)3][PW12O40]·CH3CN·H2O based on Keggin-type phosphotungstate, has been synthesized in acetonitrile at moderate temperature and then characterized by IR and single-crystal X-ray structural analysis. The crystal is of monoelinie system, space group P21/n with a = 20.489(4), b = 17.249(3), c = 23.723(4) A,β = 95.114(2)°, V =8350(3) A3, Mr= 3710.79, Z = 4,Dc= 2.952 g/cm3,F(000) = 6676,μ = 16.808 mm-1, the final R= 0.0551 and wR = 0.1269 for 9460 observed reflections with Ⅰ 20(Ⅰ). Interestingly, it is found that the structure unit contains two different cations of [C16H36N] and [Cu(2,2-bipy)3]2 .     

Multifunctional Polyoxometalate Platforms for Supramolecular Light-Driven Hydrogen Evolution**

Multifunctional supramolecular systems are a central research topic in light-driven solar energy conversion. Here, we report a polyoxometalate (POM)-based supramolecular dyad, where two platinum-complex hydrogen evolution catalysts are covalently anchored to an Anderson polyoxomolybdate anion. Supramolecular electrostatic coupling of the system to an iridium photosensitizer enables visible light-driven hydrogen evolution. Combined theory and experiment demonstrate the multifunctionality of the POM, which acts as photosensitizer/catalyst-binding-site^[1] and facilitates light-induced charge-transfer and catalytic turnover. Chemical modification of the Pt-catalyst site leads to increased hydrogen evolution reactivity. Mechanistic studies shed light on the role of the individual components and provide a molecular understanding of the interactions which govern stability and reactivity. The system could serve as a blueprint for multifunctional polyoxometalates in energy conversion and storage.     

Combination of Lindqvist-type Tungstovanadates and Transition Metal Clusters under Hydrothermal Conditions

<正>Two novel organic-inorganic heteropolyoxometalate compounds [{Cu(1,10- phen)OH}_2]_2[V_2W_4O_19]·6H_2O (1) and [Co(1,10-phen)_3]_2[V_2W_4O_(19)]·5H_2O (2) (1,10-phen = 1,10- phenanthroline) were hydrothermally synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Compound 1 contains a di-V substituted classical Lindqvist-type polyanion [V_2W_4O_(19)]~(4-), two dinuclear copper cations [{Cu(1,10-phen)OH}_2]~(2+) and six water molecules of crystallization. Two dinuclear copper cations [{Cu(1,10-phen)OH}_2]~(2+) consist of four transition metal coordination cations {Cu(1,10-phen)}~(2+), bridged by four hydroxyl groups. Meanwhile, both two dinuclear cations are grafted on the Lindqvist polyanion [V_2W_4O_(19)]~(4-) through two terminal oxygen (O(9)) and two μ_2-oxygen (O(6)) atoms. Such an unusual linking fashion is unique in the polyoxometalate chemistry. The basic framework of 2 is similar to that of 1 and contains one Lindqvist-type polyanion [V_2W_4O_(19)]~(4-), two six-coordinated cobalt cations [Co(1,10-phen)_3]~(2+) and five free water molecules.     

基于1,10-邻菲罗啉-5,6-二酮和Keggin型多金属氧化物的化合物的水热合成及性质

在水热条件下,用1,10-邻菲罗啉-5,6-二酮(Do)作为中性配体合成了3个基于Keggin型多金属氧化物的化合物(HDo)₆(PW₁₂O₄₀)₂·H₂O(1),[Cu(Do)₂(H₂O)]₂[Cu(Do)₂(PW₁₂O₄₀)(H₂O)](PW₁₂O₄₀)(2)和[Pb(Do)₂(PW₁₂O₄₀)](HDo)(3),并对其进行了元素分析、红外光谱、电感耦合等离子体分析、Ｘ射线光电子能谱、热重分析以及荧光光谱等表征。单晶X射线衍射分析表明化合物1和2为零维结构,化合物3是一维链状结构。     

银配合物[Ag_(10)(NCA)_4(PW_9~ⅥW_3~ⅤO_(40))(H_2O)_4]的合成、结构与性质

在水热条件下,制备了一种基于Keggin型多金属氧酸盐的银配合物[Ag_(10)(NCA)_4(PW_9~ⅥW_3~ⅤO_(40))(H_2O)_4].通过元素分析、红外光谱和X-射线单晶衍射方法确定了该配合物的晶体结构.在合成过程中,3-(2-吡啶羧酸)酰胺-吡嗪配体(L)分解成烟酸NCA.结构分析表明:该化合物属于三斜晶系,P_1空间群,晶胞参数a=1.188 74(9)nm,b=1.249 50nm,c=1.411 03(10)nm,α=73.712(2)°,β=66.720(2)°,γ=83.467(2)°,V=1.847 9(2)nm~3,Z=1,R_1=0.073 1,ωR_2=0.197 4.配合物中含有一种六核银亚单元[Ag_6(NCA)_4]~(2+),不同亚单元间通过配位水的氧原子连接形成一维双链结构,而一维双链进一步通过Ag—N键连接形成二维层状结构,二维层则通过[PW_9~ⅥW_3~ⅤO_(40)]~(6-)多阴离子形成最终的三维金属有机框架.标题配合物修饰的碳糊电极对H_2O_2和KNO_2还原有好的电催化活性,而且该配合物对降解亚甲基蓝、罗丹明B分子有较高的光催化效率.