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.     

两个多钒盖帽的Keggin型多铌钒酸盐衍生物的水热合成与表征

通过水热方法合成了2个由多铌酸盐和过渡金属配合物形成的有机-无机杂化配合物[Cu(TETA)]₄[VNb₁₂(VO)₄O₄₀][OH]·10H₂O(1)和[Cu(TETA)]₄[VNb₁₂(VO)₆O₄₀][OH]₅·5H₂O(2)(TETA=三亚乙基四胺). 化合物1和2的多阴离子分别是由4个{VO₅}帽和6个{VO₅}帽加盖在Keggin型多铌酸盐的方形缺口上形成的, 它们通过多酸阴离子中Nb-O_t (O_t =端氧)与[Cu(TETA)]²⁺配合物的金属中心配位构筑形成三维结构. 价键计算结果表明, Keggin中心的钒为+5价, 帽位的钒为+4价, X射线光电子能谱分析(XPS)结果也证实了这一结论. 通过单晶X射线衍射分析、红外光谱(IR)、粉末X射线衍射(PXRD)、热重(TG)分析和元素分析对这2个化合物的结构和性质进行了表征.     

一系列基于杂多酸构筑的配合物的合成,晶体结构及光催化性能

通过引入菲咯啉衍生物配体并改变反应体系中的金属盐,得到了3个新的含有杂多酸的金属-有机配合物（MOCs）,{[Cu₂（Do）₂（H₂O）₄(SiW₁₂O₄₀)]·10H₂O}_n（1）,[Ag₃（Do）₅][Ag（Do）₂](SiW₁₂O₄₀)（2）,[Cu₂（Do）₄（H₂O）₂Cl](PMo₁₂O₄₄)·2CH₃OH（3）（Do=1,10-菲咯啉-5,6-二酮）。在配合物1中,Keggin型杂多酸与Cu（Ⅱ）连接形成了二维网状结构。配合物2中的Ag（Ⅰ）显示了多种不同的配位模式,构建了一个新颖的线性三核簇状结构。在配合物3中,Cu（Ⅱ）通过氯原子连接形成了一个双核结构。结构多样性表明金属离子与第二配体Do在构建不同结构的POMs中起到很重要的作用。光催化研究表明,配合物3不仅能在UV光照射下有效地催化降解罗丹明B（RhB）,而且很稳定,能够从反应体系中分离以循环利用。     

一系列基于杂多酸构筑的配合物的合成, 晶体结构及光催化性能

通过引入菲咯啉衍生物配体并改变反应体系中的金属盐, 得到了3个新的含有杂多酸的金属-有机配合物(MOCs), {[Cu₂(Do)₂(H₂O)₄(SiW₁₂O₄₀)]·10H₂O}_n (1), [Ag₃(Do)₅][Ag(Do)₂](SiW₁₂O₄₀;2), [Cu₂(Do)₄(H₂O)₂Cl](PMo₁₂O₄₄)·2CH₃OH (3)(Do=1, 10-菲咯啉-5, 6-二酮)。在配合物1中, Keggin型杂多酸与Cu(Ⅱ)连接形成了二维网状结构。配合物2中的Ag(Ⅰ)显示了多种不同的配位模式, 构建了一个新颖的线性三核簇状结构。在配合物3中, Cu(Ⅱ)通过氯原子连接形成了一个双核结构。结构多样性表明金属离子与第二配体Do在构建不同结构的POMs中起到很重要的作用。光催化研究表明, 配合物3不仅能在UV光照射下有效地催化降解罗丹明B(RhB), 而且很稳定, 能够从反应体系中分离以循环利用。     

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.     

一系列具有CHA结构的过渡金属取代磷酸铝的合成与表征

自从1982年.美国联合碳化公司开发出一系列磷酸铝微孔化合物(AlPO4-n)以来,人们利用水热、溶剂热以及离子热技术,已经有200余种不同结构类型的磷酸铝开放骨架化合物被合成出来[2-3].     

Hydrothermal Synthesis,Structure and Magnetic Property of a Novel Hexa-Ni~Ⅱ Substituted Polyoxometalate

A novel hexa-NiⅡ substituted trilacunary Keggin polyoxometalate [{Ni6（μ3- OH）3（en）3（H2O）6}（B-α-PW9O34）]-6H2O 1 （en = ethylenediamine） has been hydrothermally synthesized and characterized by IR spectra, elemental analysis, thermogravimetric analysis （TGA）, single-crystal X-ray diffraction and magnetic property. Compound 1 crystallizes in the hexagonal space R3c with a = 20.4124（5）, c = 21.4427（4）A, γ = 120.000°, V = 7737.5（3）A3, Z = 6, GOF = 1.083, R （wR） = 0.0317 （0.0610）. Single-crystal X-ray diffraction indicates that 1 contains a hexa-Nin substituted trivacant Keggin [{Ni6（μ3-OH）3（en）3（H2O）6}（B-α-PW9O34）] unit. The magnetic study shows the presence of ferromagnetic coupling interactions within hexa-Nin clusters with J1 = 0.69 cm-1 and J2 = 0.92 cm^-1 for 1.     

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.     

一种新的二帽Keggin多金属氧酸盐的合成、表征及磁性

在水热条件下合成了一种新的二帽二支撑的Keggin型钼钒多金属氧酸盐[Cu(2,2'-bpy)₃]{[Cu(2,2'-bpy)₂]₂HP^ⅤMo8VIV6IVO₄₂]}·2H₂O(1,bpy=联吡啶),利用元素分析、红外光谱、X射线光电子能谱,粉末和X射线单晶衍射等分析技术对化合物的晶体结构进行了表征。 结果表明,该化合物属于单斜晶系,C2/c空间群,a=2.8734(3) nm,b=1.47333(12) nm,c=2.31023(16) nm,β=112.509(5)°,V=9.0351(12) nm³,Z=1,R₁=0.0489,wR₂=0.1286。 化合物的阴离子是二帽α-Keggin结构P/Mo/V多金属氧簇,通过簇阴离子两个钒帽上的端氧分别支撑两个铜过渡金属配合物,化合物簇阴离子,水分子和2,2'-联吡啶分子之间通过π-π和氢键作用形成了三维超分子结构。     

两个具有相似{V10}狚阴离子骨架的化合物的合成和结构表征

本文描述了两个具有相似阴离子骨架的化合物,犤Na2(H2O)10(NH4)4犦犤V10O28犦(1)和犤Na2(H2O)10(NH4)4犦犤V9MoO28犦(2)。化合物1的阴离子是一个常见的钒十骨架,而化合物2与化合物1是同晶异质体,化合物2的阴离子是混有一个钼原子的钒十骨架。X-射线晶体结构测定表明,这两个化合物均属于三斜晶系,P1珔空间群。晶胞参数分别为化合物1:a=0.86024(4)nm,b=1.04561(5)nm,c=1.12828(4)nm,α=68.833(1)°,β=87.158(1)°,γ=67.065(1)°;化合物2:a=0.86511(3)nm,b=1.04549(5)nm,c=1.12446(5)nm,α=69.071(1)°,β=87.145(1)°,γ=66.982(1)°。     

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.     

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.     

他克林及其衍生物的合成与表征

以廉价的靛红为起始原料,经靛红-3-肟和邻氨基苯甲腈两个中间体合成了他克林,并对其进行衍生化合成。所有新化合物的结构均经^1H NMR,IR,MS和元素分析确证。     

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.     

Hydrothermal Syntheses and Characterization of Two 1D Chain Complexes and Tetra-capped Keggin Clusters

Two new compounds, [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₆Mo^V₂V^IV₈O₄₀(SiO₄)]}[(NH₂)₂(C₂H₄)₂NH]·2H₂O(1) and [Ni(en)₂]{[Ni(en)₂]₂[Mo^VI₅Mo^V₃V^IV₈O₄₀(VO₄)]}(en)·H₂O(2)(en=ethylenediamine), have been hydrothermally synthesized and characterized by elemental analysis, infrared(IR), X-ray photoelectron spectroscopy(XPS), electron spin-resonance(ESR) and thermogravimetric(TG) analysis and single-crystal X-ray diffraction(XRD) analysis. Both the compounds exhibit a 1D chain composed of bi-supporting tetra-capped Keggin clusters and nickle coordination fragments. The 1D chains are further assembled into a 3D supramolecular network with different packing modes via hydrogen bonds. The magnetic susceptibility of compound 1 demonstrates the presence of antiferromagnetic interactions.     

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.     

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.     

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．