Target Syntheses of Two New Bivanadyl Capped Keggin Polyoxometalate Derivatives

Two new bivanadyl capped Keggin polyoxometalate-based inorganic–organic hybrid compounds, [M(2,2′-bipy)₂(H₂O)]₂[AsMo₁₂O₄₀(VO)₂]}(M = Co 1, Zn 2; bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Li₃[AsMo₁₂O₄₀] · nH₂O as starting materials. Single crystal X-ray analysis revealed that compounds 1 and 2 were isostructural, consisting of a neutral bivanadyl capped Keggin POMs bigrafted by [M(2,2′-bipy)₂(H₂O)]²⁺ fragments. Other characterizations by elemental analysis, IR spectra, XPS spectra, power X-ray diffraction and TG analysis were also described in the paper. The study of the electrochemical properties of compounds 1 and 2 exhibit similar redox behaviors, undergoing three two-electron reversible redox processes, and the electrocatalysis of 1 has also been studied in detail. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hydrothermal Synthesis and Structural Characterization of two Hybrid Keggin-based Polyoxometalates

Two new hybrid polyoxotungstates, [Co（2,2＇-bipy）3][a-H5PW11CoO40]-3H2O 1 and [Fe（2,2＇-bipy）3]2[a-HBW12O40]-2.5H2O 2 （2,2＇-bipy = 2,2＇-dipyridyl）, have been hydrothermally synthesized and characterized by IR, TGA and single-crystal X-ray structural analyses. The results of X-ray crystallography analyses exhibit that 1 consists of one a-Keggin anion [a-H5PW11CoO40]2- and one isolated [Co（2,2＇-bipy）3]2＋ complex, while 2 is constructed from one a-Keggin anion [a- HBW12O40]4- and two isolated [Fe（2,2＇-bipy）3]2＋ cations. The data for 1： orthorhombic system, space group Pbcn, a = 16.062（6）, b = 27.278（10）, c = 16.951（6）A, V = 7427（5）A3 and Z = 4; and those for 2： triclinic system, space group P1, a = 13.787（3）, b = 17.857（5）, c = 18.918（5）A, a = 88.009（12）, β = 72.768（10）, γ = 74.935（10）°, V = 4291（2）A3 and Z = 2.     

Syntheses and Characterizations of Two New Coordination Polymers Based on Dicarboxylate and Nitrogen-contained Mixed Ligands

Two new carboxylate coordination polymers [Ni(2,3'-oba)(bib)]n] and [Mn(2,4'-oba)(bib)0.5]n(2,3'-oba = 2-(3-carboxyphenoxy)benzoic acid,2,4'-oba = 2-(4-carboxyphenoxy) ben-zoic acid and bib = 1,4-bis(2-methyl-imidazol-yl)butane) have been synthesized and characterized by elemental analysis,IR and X-ray single-crystal diffraction studies.Compound 1 crystallizes in monoclinic,space group P21/c,while compound 2 in the triclinic space group P.Compound 1 displays a one-dimensional ladder-like chain.The dinuclear paddle-wheel secondary building units(SBUs) constructed by four 2,4'-oba2-ligands in compound 2 are linked by bib into a 2D(4,4) layer structure.     

Influence of metal ions on the structures of Keggin polyoxometalate-based solids: Hydrothermal syntheses, crystal structures and magnetic properties

Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen)₂]₂{[Cu(phen)]₂ [SiMo₁₂O₄₀(VO)₂]} (1), {[Zn(phen)₂]₂[GeMo₁₂O₄₀(VO)₂]}{[Zn(phen)₂(H₂O)]₂ [GeMo₁₂O₄₀(VO)₂]}·3H₂O (2) and {[Co(phen)₂]₂[PMo₁₂O₄₀(VO)₂]}{[Co(phen)₂(OH)]₂ [PMo₁₂O₄₀(VO)₂]}·2.5H₂O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo₁₂O₄₀(VO)₂] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo₁₂O₄₀(VO)₂]²⁻ linked to two [Cu(phen)]⁺ complexes with two [Cu(phen)₂]⁺ countercations. Compound 2 contains two bicapped Keggin anions [GeMo₁₂O₄₀(VO)₂]⁴⁻, one linked to two [Zn(phen)₂(H₂O)]²⁺ cations and the other one linked to two [Zn(phen)₂]²⁺ cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo₁₂O₄₀(VO)₂]⁴⁻ connected by [Co(phen)₂]²⁺ cations. Discrete bicapped Keggin anions [PMo₁₂O₄₀(VO)₂] linked to two [Co(phen)₂(OH)]⁺ cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions.     

Supramolecular assembly of organic bicapped Keggin polyoxometalate

Two novel supramolecular assemblies of organic bicapped Keggin polyoxometalates (pbpy)₈H₃[PW₁₂O₄₀]·2H₂O (1) and (pbpy)₄H[PMo₁₂O₄₀(VO)] (2) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Crystallographic data for compound (1), C₁₂₈H₁₀₃N₁₆O₄₂PW₁₂, triclinic, space group : a=13.4759(8) Å, b=14.6395(11) Å, c=16.5743(10) Å, α=95.764(2)°, β=102.166(2)°, γ=92.9870(10)°, Z=1, V=3171.1(4) Å³; for compound (2), C₆₄H₄₉N₈O₄₁PMo₁₂V, triclinic, space group : a=11.5377(11) Å, b=12.7552(8) Å, c=14.9599(10) Å, α=72.270(4)°, β=88.916(2)°, γ=67.865(4)°, Z=1, V=1931.0(3) Å³. X-ray analyses show that both 1 and 2 represent rare organic bicapped Keggin structures and are supported by supramolecular interactions to extend into a 3D framework. In particular, the unusual structure feature of compound 2 contains a simultaneously organic and inorganic capped structure.     

苯并咪唑修饰的2个Keggin型多酸基化合物的合成与晶体结构

利用水热合成方法合成了2个新的苯并咪唑修饰的Keggin型多酸基化合物[(C_7H_6N_2)_3(H_3PMo_(12)O_(40))]·H_2O(1)和[KNa_2(C_7H_5N_2)_2(H_(2.5)Si W_(12)O_(40))_2]·6(C_7H_6N_2)(2)(C_7H_6N_2=苯并咪唑).化合物1为超分子结构,化合物2为2种碱金属钾和钠与多酸配位形成链状多酸基化合物,并通过元素分析和X-射线单晶衍射方法确定了2种化合物的晶体结构.单晶结构分析表明化合物1属于三斜晶系,P-1空间群,晶胞参数a=1.1580(7)nm,b=1.3159(8)nm,c=1.8254(12)nm,α=84.418(10)°,β=88.958(10)°,γ=65.852(10)°,V=2.5255(3)nm3,Z=2;化合物2也属于三斜晶系,P-1空间群,晶胞参数a=1.3586(9)nm,b=1.4403(10)nm,c=1.8365(13)nm,α=109.509(10)°,β=90.755(10)°,γ=114.864(10)°,V=3.0236(4)nm3,Z=1.     

新型超分子化合物[H_2N(CH_2)_6NH_2](H_3O)_4[PMo_7~(VI)Mo_5~VO_(40)(V~(IV)O)_2]晶体的水热合成与表征

在水热条件下合成了一种新型超分子化合物,通过元素分析、红外光谱、热重分析和X射线单晶衍射方法确定了其晶体结构.结构分析表明:该晶体属于单斜晶系,C2/m空间群,晶胞参数:a=1.2643(3)nm,b=2.1069(4)nm,c=1.0057(2)nm,α=90°,β=110.16(3)°,γ=90°,V=2.5149(9)nm3,Z=2,R1=0.0618,wR2=0.1794.     

pH-controlled assembly of two new supramolecular hybrid compounds based on Keggin polyoxotungstates

Two supramolecular compounds based on Keggin polyoxotungstates, (4,4′-H₂bpy){[Cu(4,4′-bpy)]₂[SiW₁₂O₄₀]} (1) and (4,4′-H₂bpy)₂[SiW₁₂O₄₀]·2H₂O (2) have been synthesized and characterized by elemental analyses, IR, UV, XPS spectra, TG analyses, and single crystal X-ray diffraction analyses. Compound 1 exhibits an infinite 1-D ladder like structure, which is further interconnected into a 3-D supramolecular framework via hydrogen bonding interactions. Compound 2 contains 4,4′-bipyridine (4,4′-bpy), pseudo-Keggin polyoxoanions [SiW₁₂O₄₀]^4?, and water molecules. Polyoxoanions together with water molecules in 2 construct a 3-D inorganic supramolecular network through O···O and O···Ow(1) interactions. The electrochemical behaviors and photocatalytic properties of 1 and 2 have been investigated.     

一种具有Keggin结构的固体杂多酸的合成及其晶体结构

以钨酸钠、氯化钴、醋酸钴及1,3-丙二胺为原料,利用水热合成法制备了一种具有Keggin结构的杂多酸H6[CoW12O40].2.5H2O;利用单晶X射线衍射分析了产物的晶体结构.结果表明,产物中的过渡金属Co2+离子作为中心原子与4个氧原子形成CoO4四面体;CoO4四面体被4个W3O13金属簇包围,与每个W3O13金属簇之间通过共顶点连接而形成[CoW12O40]6-阴离子;六个氢离子作为抗衡阳离子,最终形成固体杂多酸分子.     

含有甘氨酸的Keggin型杂多蓝的合成和抗艾滋病毒(HIV-1)活性研究

采用控制电位电解方法,制得8种含有甘氨酸的Keggin型钨系杂多蓝配合物．通过IR,UV-vis,^H NMR,^183W NMR,XPS等方法对其结构进行了表征．这类化合物具有较强的抗碱解能力．在MT4细胞内,对合成化合物进行了抗艾滋病毒(HIV-1)活性及毒性测定,发现该类化合物的抗艾滋病毒(HIV-1)活性随着还原电子数增多有增强的趋势,其中含有甘氨酸的十二钨锗酸4电子杂多蓝(代号HPBG-110)有较高的治疗指数(TI)．初步的试验结果表明：该类化合物的抗HIV-1活性作用是在病毒感染早期,通过抑制艾滋病毒(HIV-1)在靶细胞表面吸附而发挥作用的．     

Hydrothermal Synthesis and Crystal Structure of a Polyoxometalate- based Complex [Cu^I（phen）2]4（SiW12O40）

A new hybrid polyoxometalate-based complex, [Cu^I（phen）214（SiW12O40） （phen = 1,10-phenanthroline）, has been synthesized by hydrothermal method and characterized with the aid of elemental analysis, IR, UV spectra and thermal analysis studies. The result of X-ray crystallography analysis exhibits that the title compound crystallizes in the orthorhombic space group P212121, and the formula is C96H64N16Cu4SiW12O40. Crystal data： a = 18.3574（14）, b = 21.1952（16）, c = 27.992（2）A, Mr = 4570.08, V = 10891.4（14）A^3, Z = 4, Dc = 2.787 g/cm^3,μ = 13.478 mm^-1, R = 0.0364, wR = 0.0638 （I 〉 2σ（I）） and F（000） = 8360. The complex consists of one α-Keggin anion [SIW12O40]^4- and four discrete [Cu^I（phen）2]^＋ cations. The valence sum calculations for the Cu atoms suggest that all four Cu atoms are in the ＋1 oxidation state.     

Syntheses,Crystal Structures and Bioactivities of Two Isatin Derivatives

The title compounds(Z)-3-(2-(3-chloropyridin-2-yl)hydrazono)indolin-2-one(A) and 7-bromo-(Z)-3-((4-pyridinyl)carboxlichydrazono)-2-indolinone(B) have been synthesized and structurally determined by elemental analysis and single-crystal X-ray diffraction studies.Compound A(C13H8ClN4O) belongs to the orthorhombic crystal system,space group Pca21 with a = 20.799(4),b = 4.9312(10),c = 11.764(2),V = 1206.6(4)3,Mr = 271.68,Dc = 1.496 g/cm3,μ = 0.313 mm-1,F(000) = 556,Z = 4,the final R = 0.0346 and wR = 0.0831 for 2683 observed reflections with I > 2σ(I).Compound B(C14H9BrN4O2) belongs to the triclinic crystal system,space group P1 with a = 6.6834(13),b = 7.0727(14),c = 14.285(3),α = 95.56(3),β = 99.00(3),γ = 102.95(3)°,V = 643.8(2)3,Mr = 345.16,Dc = 1.780 g/cm3,μ = 3.203 mm-1,F(000) = 344,Z = 2,the final R = 0.0487 and wR = 0.1167 for 2334 observed reflections with I > 2σ(I).The preliminary herbicidal bioassay reveals that compounds A and B have some inhibition both in vivo and in vitro against AHAS.     

Hydrothermal Synthesis and Crystal Structure of a New Hexa-cobalt-containing POM

A new compound Na3H3[Co（en）3]2[Co4（H2O）2（PW9O34）2]·11H2O 1 （en = ethylenediamine） has been synthesized under hydrothermal conditions and characterized by IR, TGA, and single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group C21c, a = 26.336（5）, b = 18.135（2）, c = 22.751（4）A, β = 123.039（7）° and Z = 4. X-ray crystallographic study on compound 1 reveals that it includes a Weakley-type sandwich polyoxoanion [Co4（H2O）2（PW9O34）2]^10-, two complex ions [Co（en）3]^2＋, three Na^＋ ions （one Na（1） and two Na（2））, and eleven crystallographic water molecules. The sandwich polyoxoanions are linked by Na2 to form 2D layers parallel to the （100） plane, and these layers are further connected by Nal along the α-axis to generate a 3D structure.     

Organophosphonotungstic HPA of Keggin Type with Sulfo,Taurine and Glycine Substituted Ethylphosphonic Acids as the Coordinate Center

Recent years, heteropoly acids (HPA)and their derivatives have received current attention due to their potential applications in analytical chemistry, catalysis, material sciences and medicine1-2. Usually, the core or coordinate center for most of the heteropoly compounds (HPC) are inorganic acids such as H3PO4, H3SiO3 etc. Although HPC with organophosphonic acids as coordinate center have been confirmed about 15 years ago, in which the molar ratio x: m for most of the heteropoly anion…     

两种有机-无机复合杂多化合物的水热合成及结构表征

利用水热法制备了基于饱和Keggin结构阴离子构筑的有机-无机复合多金属氧酸盐(4,4′-bipy)4H4[PMo12O40](CH3COO).1.5H2O(1)和(4,4′-Hbipy)2(4,4′-bipy)2H[PW12O40].3.5H2O(2)(4,4′-bipy=4,4′-联吡啶),并借助元素分析、红外光谱、紫外光谱、热分析和X射线单晶衍射分析了两种化合物的组成和结构.结果表明,化合物1和2均属于单斜晶系,P2(1)/c空间群.化合物的晶胞参数为:a=1.869 40(13)nm,b=1.404 23(9)nm,c=2.707 76(18)nm,β=105.848 0(10)°,V=6.837 9(8)nm3,Z=4,R1=0.095 4;化合物2的晶胞参数为:a=1.884 80(12)nm,b=1.409 89(9)nm,c=2.664 92(17)nm,β=105.368 0(10)°,V=6.828 4(8)nm3,Z=2,R1=0.097 2.两种化合物结构类似,其结构单元均是由饱和Keggin阴离子与游离的4,4′-联吡啶分子通过静电作用相结合形成的.     

沙漏型砷钼酸盐(NH_4)_7[AsMo_8O_(30)]的水热合成,结构和性质(英文)

利用水热合成法制备了一种新的沙漏型砷钼酸盐化合物(NH_1)_7[AsMo_8O_(30)](1),借助X射线单晶衍射、X射线粉末衍射、红外光谱(IR)、紫外光谱(UV)和热分析研究了化合物的结构和性质.结果表明,化合物1属于正交晶系,Cmcm空间群,晶胞参数为:a=0.848 3(4)nm,b=2.322 3(10)nm,c=1.559 1(7)nm,V=3.071(2)nm~3,Z=4,R_1[I>2σ(I)]=0.0431,ωR_2[I>2σ(I)]=0.123 6.X射线单晶衍射分析结果表明,化合物1包含沙漏型的砷钼酸盐阴离子[AsMo_9O_(30)]~(7-).     

一维锯齿状化合物[(en)2(Mo6O20H4)]n的水热合成及晶体结构

利用Na2MoO4·2H2O,MoO3,乙二胺,和H2O通过水热合成法合成了一维锯齿状化合物[(en)2(Mo6O20H4)]n.晶体解析表明,该化合物属于单斜晶系,P21/n空间群,a=0.80680(16)nm,b=1.4371(3)nm,c=0.88874(18)nm,β=97.89(3)°,V=1.0207(4)nm3,Z=2,Dc=3.305Mg·m-3,μ=3.681mm-1,F(000)=960.该化合物结构单元由二个游离的乙二胺分子和一个阴离子Mo6O4-20阴离子中,六20构成.在Mo6O4-个钼原子和八个相邻的氧原子构成两个八员环,在每个八员环的两侧分别存在着一个与三个钼原子相连的桥氧.     

由Keggin型簇和过渡金属配合物构筑的杂多钨酸盐锯齿链的合成和结构

采用水热法合成了一维锯齿链状的有机-无机杂化杂多钨酸盐[Cu（en）2（H2O）]{[Cu（en）2（H2O）][Cu（en）2]（α-SiW12O40）}（OH）2·H2O（记作1;en=1,2-乙二胺）;利用元素分析、红外光谱和X射线单晶衍射对其结构进行了表征.结果表明,化合物1属于三斜晶系,P-1空间群;其晶格参数为：a=1.297 6（6）nm,b=1.473 5（7）nm,c=1.909 9（9）nm,α=86.736（8）°,β=88.833（8）°,γ=74.840（8）°,V=3.519（3）nm3,Z=2.就分子结构而言,化合物1由一个常见的Keggin型多阴离子[α-SiW12O40]4-、两个不同的铜配位阳离子[Cu（en）2（H2O）]2＋和[Cu（en）2]2＋、一个游离的铜配位阳离子[Cu（en）2（H2O）]2＋、两个氢氧根离子和一个结晶水组成;相邻的[α-SiW12O40]4-多阴离子通过两个配位阳离子[Cu（en）2）]2＋相连,形成一维锯齿链状结构.     

新型笼状钼磷超分子化合物的水热合成与晶体结构

用水热法首次合成了含有２ 种有机胺的新型笼状钼磷超分子化合物〔ＮＨ３（ＣＨ２）６ＮＨ３〕７〔ＮＨ３（ＣＨ２）２ＮＨ３〕２（Ｈ３Ｏ）６〔Ｐ２ Ｍｏ５Ｏ２３〕４·１１Ｈ２Ｏ,并通过元素分析、红外和Ｘ－ 射线单晶衍射法进行了结构表征．晶体属三斜晶系,空间群ｐ１杂多阴离子中的每个〔Ｐ２Ｍｏ５Ｏ２３〕６－ 是由５ 个ＭｏＯ６ 八面体和两个ＰＯ４ 四面体键合而成,其中Ｍｏ,Ｐ原子成一个畸变五角双锥构型．     

三维超分子化合物(H2bimb)2(SiW12O40)的水热合成与晶体结构

利用水热合成方法合成了1个新的Keggin基质的超分子化合物(H2bimb)2(SiW12O40),并通过元素分析、红外光谱、热重分析和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三斜晶系,P-1空间群,晶胞参数a=1.122 6(5)nm,b=1.563 5(5)nm,c=1.892 7(5)...