A novel one-dimensional organic-inorganic polymer: synthesis and crystal structure of [{Ca(DMF)<Subscript>5</Subscript>}<Subscript>2</Subscript>SiMo<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Subscript>η</Subscript>

A novel polyoxometalate-based organic-inorganic polymer [Ca(DMF)_{5 2}SiMo₁₂O₄₀]_η has been synthesized and characterized by elemental analysis, IR, UV and X-ray single-crystal structural analysis. The title compound crystallizes in a monocline lattice, P2₁/n, with a =1. 3379 (3),b = 1. 9796 (4), c = 1. 4574 (3) nm, β= 92.24(3)δ,V= 3. 8568 (13) nm³, Z = 2,R ₁ = 0.083 andRw= 0. 2065. The result of crystal structure analysis indicates that Ca²⁺ is surrounded by seven coordination oxygen atoms with pentagonal bipyramidal geometry and bridged with terminal oxygen atom of polyanion in the structure. The compound contains an unprecedented one-dimensional linear chain built by alternate polyanions and cationic units through Mo-O_d-Ca-O-Ca links in crystal. The IR spectra and X-ray crystallography analysis exhibit that there is a strong interaction between the polyanion and organic group in solid state. The electronic spectra (λ= 200–500 nm) for the title compound dissolved in the mixed solvent of acetonitrile and water indicate that it is fully dissociated. The TGA/DTA study shows three stages of weight loss and that the thermal stability of polyanion is better than that of H₄SiMo₁₂O₄₀ · H₂O.     

新型—维锯齿链状聚金属氧酸盐配位聚合物［｛La(DMSO)_6(H_2O)}·(PMo_(12)O_(40))·H_2O］_n的合成、结构及表征

以a-H_3PMo_(12)O_(40)·nH_2O, La_2O_3和二甲基亚砜（DMSO）为原料，在 乙腈和水的混合溶剂中制得了一维锯齿链状配位聚合物［｛La(DMSO)_6(H_2O)}· (PMo_(12)O_(40))·H_2O］_n,X射线单晶衍射结果表明，聚合物中金属配阳离子与 杂多阴离子骨架通过Mo-O_d-La-O_d-Mo相连并形成一维无限链，每一个不对称结构 单元中含一个结晶水，La~(3+)的配位数为九，三帽三棱柱构型，配位氧原子分别 来自6个DMSO分子，1个H_2O分子和2个相邻杂多阴离子的端氧，晶体氧于单斜晶系 ，P2_1/c空间群，a=1.3916(3)nm,b=1.7058(3)nm,c=2.4750(5)nm,β=99.16(3)~° ,Z=4,V=5.800(2)nm~3,D_c=2.825g/cm~3,R_1=0.0446,wR_2=0.0871,IR光谱和X射线 单晶衍射结果一致表明，在固态条件下配阳离子和杂多阴离子之间存在相互作用， UV光谱表明，在稀的水溶液中，由于溶剂化作用，杂多阴离子与配阳离子处于解离 状态，热性质研究表明，形成标题化合物后，杂多阴离子的热稳定性与磷钼酸相比 明显增强。     

三维超分子化合物[Ni（DMF）6]2[SiMo12O40]·H2O的合成、晶体结构及表征

合成了一个新的三维超分子化合物[Ni（DMF）6]2[SiMo12O40]·H2O,通过红外光谱、X射线单晶衍射和热重分析等手段对其结构进行了表征．单晶结构解析结果表明,标题化合物属于三方晶系,船空间群,晶胞参数为：a=1．5902（4）nm,b=1．5902（4）nm,c=3．2281（17）nm,V=7．069（4）nm^3,Z=3,Dc=1．994g／cm^3,μ=2．032mm^-1．F（000）：4146,R1=0．0516,ωR2=0．1453．配合物中镍离子采用6配位的八面体配位构型,晶体堆积中通过多种分子间氢键作用形成三维网状结构．     

[Cu（Dfo）3]2+修饰的Keggin型超分子化合物的合成与晶体结构

利用水热合成方法合成了1个新的Keggin基有机-无机杂化化合物[Cu2(Dfo)6(SiMo12O40)],并通过元素分析、红外光谱和X射线单晶衍射方法确定了该化合物的晶体结构.结构分析表明该化合物属于立方晶系,Pa-3空间群,晶胞参数a=b=c=2.081 82(3)nm,α=β=γ=90°,V=9.022 6(4)nm3,Z=4,R1=0.064 9,ωR2=0.156 1.将目标化合物制成碳糊电极,利用循环伏安法研究了其电化学行为及其对NO2-还原的电催化性能.     

簇合物{[Ni(enMe)2][SiW12O40]}[Ni(enMe)2(H2O)2]2·3H2O的水热合成及晶体结构

用水热法合成出一种新的一维链状簇合物{[Ni(enMe)2][SiW12O40]}[Ni(enMe)2(H2O)2]2·3H2O, 并对其进行了元素分析、IR谱、TGA及X射线单晶衍射等系列表征. 该晶体属于单斜晶系, 空间群C2/c, a=1.2656 nm, b=2.20656(4) nm, c=2.26763(4) nm, β=92.078°, V=6.32852(16) nm3, Z=4, Dc=3.801 g/cm3, μ=2.271 mm-1, F(000)=6512, R1=0.0549, wR2=0.1087. 在该化合物中, 具有α-Keggin结构的聚阴离子簇[SiW12O40]6-之间通过配位阳离子[Ni(enMe)2]2+桥连成一维无限链状结构, 另一种配位阳离子[Ni(enMe)2(H2O)2]2+和水分子填充在结构中, 通过分子间的氢键作用将该化合物拓展为三维网状结构.     

Synthesis,Structure Characterization and Biological Activity of a Novel Amino Acid Salt(HAla)_8(H_3O)_(10)[PMo_(12)O_(40)]_6·22H_2O

A novel compound was synthesized and characterized by means of elemental analysis, IR and UV spectra, TG, CV and single crystal X-ray diffraction. The compound crystallized in an orthorhombic space group C222 with a = 1. 622 4(3) nm, b=3. 498 4(7) nm, c=l. 301 5(3) nm,V=7. 387(3) nm3, Z = 6, R1 = 0. 037 3, wR2 = 0. 114 0. The Ala (Ala = alanine) molecules were protonated at the amino nitrogen N (1) and the C (2) of Ala group with the terminal oxygen atom O(15), O(14), O(26) and O(27) of the polyoxometalates participating in the hydrogen bond network. The anti-tumor activity of the title compound was estimated against Hela and Pc-3m cancer cells.     

二正丁基锡水杨醛缩对氨基苯甲酸酯配合物的合成、表征及结构研究

The title complex {[ⁿBu₂Sn(2-OHC₆H₄CH=NC₆H₄COO)]₂O}₂·2H₂O was synthesized by the reaction of N-(4-carboxyphenyl)-salicylideneimine with dibutyltin(IV) oxide in 1∶1 molar ratio. The compound has been characterized by elemental analysis, IR, ¹H NMR spectra and X-ray single crystal diffraction. It crystallizes in triclinic system with space group P1. The crystal data are: a=1.242 9(2) nm, b=1.261 3(2) nm, c=1.594 9(3) nm, α=102.06(2)°, β=92.884(3)°, γ=95.939(3)°, Z=2, D_c=1.342 g·cm^-3, F(000)=1 000, V=2.425 2(7) nm³, R₁=0.041 5, wR₂=0.104 4. The compound is in centro-symmetric dimer structure mode with a four-member central endo-cyclic Sn₂O₂ unit in which the bridging oxygen atoms are tri-coordinated. All the tin atoms are five-coordinated with geometry of distorted trigonal bipyramid. CCDC:286105.     

有机-无机复合物[Cu（en）（H_2O）（2,2-′bipy）]_2H_3[BW_（12）O_（40）]·2.5H_2O的水热合成、结构及性质

利用水热合成方法制备了组成为[Cu（en）（H2O）（2,2′-bipy）]2H3BW12O4.02.5H2O的多金属氧簇有机-无机复合物,并用元素分析、IR和UV光谱、XPS、TG、荧光光谱、X射线单晶衍射对化合物进行了表征和性质研究.该化合物属于单斜晶系,P2（1）/c空间群,a=1.951 1（2）nm,b=1.229 76（12）nm,c=2.505 9（3）nm,β=91.266（2）°,V=6.011 1（11）nm3,Z=4.化合物阴离子[BW12O40]5-与配位阳离子[Cu（en）（H2O）（2,2′-bipy）]＋通过静电作用相结合.XPS表明化合物中Cu、W氧化态分别为＋1和＋6价.     

电荷转移盐[C5H10NO]3[PW12O40]·C5H9NO·3H2O的合成和晶体结构

由N-甲基吡咯烷酮和H3PW12O40·nH2O反应得到了标题化合物,并以元素分析,红外光谱,质谱和X射线单晶衍射对其结构进行了表征．结构解析表明,该化合物属于三斜晶系,Pi空间群,晶胞参数为：α=1．335（2）nm,b=1．374（2）nm,c=1．826（2）nm,α=98．92（2）°,β=107．7（2）°,γ=109．9（2）°,V=2．873（1）nm^3,Z=2,Dc=3．840Mg/m^3,μ=24．05mm^-1,F（000）=2926,R1=0．0632,wR2=0．1403．在该化合物中,杂多阴离子仍保持其Keggin结构,通过静电引力与阳离子作用．     

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5- as building blocks

A two-dimensional network compound [Ce(DMF)4(H2O)][α-BW12O40]·H2O·(HDMA)2 (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H5BW12O40·nH2O, Ce(NO3)3·6H2O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P21/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R1 = 0.07710, wR2 = 0.1416. Structural analysis indicates that every [Ce(DMF)4(H2O)]3-building block is surrounded by three adjacent [α-BW12O40]5-polyanions, meanwhile, every [α-BW12O40]5-polyanion interconnects with three neighboring [Ce(DMF)4(H2O)]3+ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560℃. The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4-7 media.     

三维配位聚合物[C4H12N2]3[PMo12O40]的合成、结构及其电化学性质

The title compound [C4H12N2] 3 [PMo12O40] was synthesized from the hydrothermal reaction and charac-terized by IR, elemental analysis and X-ray signal crystal structural analysis. The crystal of the title complex belongs to trigonal space group R3c with a=1.788 62 nm, c=2.354 3 nm, and V=6.522 62 nm3, Z=6, R1=0.038 4, wR2=0.102 0. The compound consisted of piperazine and PMo12O403-, and the structure is extended to three dimensional framework owing to the hydrogen bond between the O atoms and N atoms. The bulk-modified carbon paste electrode (APM-CPE) using this compound as modifier shows a good electrocatalytic activity toward the oxidation of ascorbic acid(AA). CCDC: 707968.     

A Novel Organic—Inorganic Complex：Synthesis and Crystal Structure of [Ca（DMSO）5（H2O）]2 SiMo12O40

It is becoming a focus to synthesize and assemble organic-inorganic materials, especially, to synthesize charge-transfer complexes formed by polyoxometalate and organic donors. They have attracted much attention because such complexes are active in their electric, magnetic and optic properties1-4, many investigations about them have been done and some crystal structures of them were reported5-6. But, the disadvantage of these crystals is instability at room temperature. According to the view…     

Synthesis and Crystal Structure of the Polyoxometalatebased Complex [Mn（DMSO）5H2O]2SiMo12O40

1 INTRODUCTION The design and assembly of organic-inorganic solid-state materials with active physical properties, such as materials with electrical, magnetic and opti- cal properties, has become a focus of a great deal of interest in recent years[1, 2].…     

Syntheses and Crystal Structures of Three Novel Amino-acid-containing Polyoxomolybdosilicates

1 INTRODUCTION Polyoxometalates as metal-oxygen cluster ions have received a great deal of research due to their potential applications in catalysis, medicine and ma- terials science[1]. The modification of organic groups to the surface of polyoxoanions gives POMs more interesting character, and many derivatives of poly- oxoanions with organic ligands have been studied[2]. Particularly the potential applications of polyoxo- metalate as drugs in anti-viral and anti-AIDS have attracted t…     

新型环形聚阴离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-的结构及表征

在pH=3.0的水溶液中，Na_2WO_4·2H_2O与NaAsO_2·6H_2O和NH_4Cl反应，得 到了新的杂多钨酸盐(MH_4)_19Na_2[{WO(H_2O)}_3(AsW_8O31)_3]·45H_2O单晶， 用X射线单晶衍射法及元素分析确定了其结构，晶体属单斜晶系，空间群C2/c，晶 胞参数为：a=3.1165(11)nm, b=1.7388(7)nm, c=2.2789(9)nm, β=97.342(6)°, V=12.248(8)nm~3, Z=4, R_1=0.0571,wR_2=0.0741[I＞2σ(I)]. 环型聚阴离子 [{WO(H_2O)}_3(AsW_8O31)_3]~21-是由三个{WO(H_2O)}桥连三个新发现的 {AsW_8O31}单元构成的，环聚离子[{WO(H_2O)}_3(AsW_8O31)_3]~21-具有近似D_ (3h)对称性。对该化合物还进行了~183W NMR, IR和TG表征。     

[4,4′-bpyH_2]_5H_2[α-P_2W_(18)O_(62)]_2·4H_2O的合成与结构表征

利用水热方法合成了一种基于双Dawson多阴离子和质子化的4,4′-联吡啶阳离子构筑的化合物[4,4′-bpyH2]5H2[α-P2W18O62]2·4H2O,并经IR光谱、元素分析、热重分析和X射线单晶衍射等测试技术进行了表征.标题化合物属于三斜晶系,P墿空间群,晶胞参数:a=1.35373(5),b=2.24256(13),c=2.73282(11)nm,α=79.890(13),β=77.568(8),γ=80.349(11)°,V=7.9029(6)nm3,Z=2,Dc=4.031g/cm3,GOOF=1.049,R1=0.0674,wR2=0.1434.结构分析结果表明,标题化合物分子由5个质子化的4,4′-联吡啶阳离子、2个H+离子、2个饱和Dawson结构多阴离子[P2W18O62]6-和4个结晶水分子组成.     

新型硅钨酸盐的水热法合成、结构表征和磁性

用水热方法合成了新型的硅钨杂多氧酸盐(C2H10N2)3(SiW12O40)·3H2O,用元素分析、IR和单晶X射线衍射分析技术对化合物的分子和晶体结构进行了表征。 结果表明,该化合物的晶体属于三斜晶系,P1空间群,a=1.3193(3) nm,b=1.3198(3) nm,c=1.3193(3) nm,α=76.05(3)°,β=76.13(3)°,γ=76.05(3)°,V=2.1231(7) nm3,Z=1,R1=0.0518,wR2=0.1355。 化合物分子由一个α-Keggin结构的硅钨多金属簇阴离子、3个乙二胺分子作为平衡阳离子和3个结晶水分子组成,簇阴离子的端氧与乙二胺阴离子及结晶水分子之间的多种类型的氢键连接形成三维超分子结构。 化合物磁性测量表明,其分子内存在反铁磁性相互作用。     

杂多酸盐Na3H8[La（PW11O39）2]·19H2O的合成与晶体结构

合成了二维层状单缺位Keggin结构阴离子稀土衍生物Na3H8[La（PW11O39）2].19H2O,并用IR和X射线单晶衍射等手段对其进行了表征.该晶体属于单斜晶系,P2/n空间群,a=1.343 43（8）nm,b=1.259 35（7）nm,c=3.541 8（2）nm,β=99.151 0（10）°,V=5.915 9（6）nm3,Z=2,R1=0.042 9,wR2=0.119 4.化合物阴离子[La（PWO）]11-通过NaO桥联形成一维链,再通过NaO桥联形成二维层状结构.     

Construction of different dimensional inorganic-organic hybrid materials based on polyoxometalates and metal-organic units via changing metal ions: from non-covalent interactions to covalent connections

Five POM-based hybrid materials have been designed and synthesized based on different metal ions under hydrothermal conditions, namely, [Zn(Hfcz)(H(2)O)(3)](H(3)fcz)(SiMo(12)O(40)).3H(2)O (1), [Cd(2)(Hfcz)(6)(H(2)O)(2)](SiMo(12)O(40)).H(2)O (2), [Co(2)(Hfcz)(2)(SiW(12)O(40))](H(3)fcz)(2)(SiW(12)O(40)).10H(2)O (3), [Ni(2)(Hfcz)(4)(H(2)O)(2)](SiW(12)O(40)).5H(2)O (4) and [Ag(4)(Hfcz)(2)(SiMo(12)O(40))] (5), where Hfcz is fluconazole [2-(2,4-difluorophenyl)-1,3-di(1H-1,2,4-triazol-1-yl)propan-2-ol]. Their crystal structures have been determined by X-ray diffraction, elemental analyses, IR spectra, and thermogravimetric analyses (TGA). There are 1D mono and double chain-like metal-organic units in compounds 1 and 2, respectively. Polyoxometalates and metal-organic units co-crystallize through hydrogen bonds. In compound 3, metal-organic sheets are pillared by one kind of polyanion through covalent connections to generate a sandwich double-sheet. The other kind of polyanion acts as a counter-ion and lies in two adjacent sandwich double-sheets through non-covalent interactions. Polyanions covalently link metal-organic sheets to extend to an unusual 3D 5-connected framework with the (4(4).6(6)) topology in 4. In compound 5, polyanions link metal-organic chains to form a sheet through covalent connections. It is interesting that compound 5 shows an intricate (4,5,10)-connected framework with (4(4).6(2))(4)(4(8).6(2))(2)(4(14).6(19).8(12)) topology based on two kinds of Ag cations as four-connected and five-connected nodes, and polyanions as ten-connected nodes, when AgO interactions are considered. It represents the highest connected network topology presently known for polyoxometalate systems. The structural differences among 1-5 indicate the importance of different metal-organic units, coordination modes of polyanions for framework formation, and the interactions between polyanions and metal-organic units. In addition, the luminescent properties of compounds 1, 2 and 5, and electrochemical behaviours of compounds 1-5 have been investigated.     

An organic-inorganic polymer with Dawson-type polyoxometalates as building blocks: synthesis,characterization and crystal structure of [{Pr(DMF)_6}{Pr(DMF)_7}(P_2W_(18)O_(62))]_n

An organic-inorganic polymer of [{Pr(DMF)6}{Pr(DMF)7}(P2W18O62)]n has been synthesized in acetonitrile-water (5:2, volume ratio) mixed solvent. Single-crystal X-ray structural analysis indicates that the title compound crystallizes in a monoclinic lattice, P21/C, with a = 1.8574(4), b = 2.3907(5), c = 2.4222(5) nm, B= 99.48(3), Z= 4, V= 10.609(4) nm3, Dc = 3.501 Mg/m3, F(000) = 9972, R1 = 0.0654 and wR2= 0.1098. The result of crystal structure analysis reveals that Pr3+(1) complex ion is eight-coordinated with a distorted bicapped trigonal prismatic environment, which is combined with the heteropolyanion by terminal oxygen atom, whereas Pr3+(2) complex ion is also eight-coordinated with a distorted square antiprismatic environment, which is linked to the heteropolyanion by terminal oxygen atom. Adjacent structure units of [{Pr(DMF)6}{Pr(DMF)7}(P2W18O62)] are bridged through W-O-Pr1-O-W links to form an unprecedented one-dimensional zigzag linear chain by alternate polyanions and cationic units in the po