0-D and 1-D inorganic-organic composite polyoxotungstates constructed from in-situ generated monocopper-substituted Keggin polyoxoanions and copper-organoamine complexes

Combination of in-situ generated monocopper^II-substituted Keggin polyoxoanions with copper^II-organoamine complexes under hydrothermal conditions results in seven inorganic-organic composite polyoxotungstates [Cu(en)₂(H₂O)]₂{[Cu(en)₂][α-PCuW₁₁O₃₉Cl]}·3H₂O (1), {[Cu(en)₂(H₂O)][Cu(en)₂]₂[α-PCuW₁₁O₃₉Cl]}·6H₂O (2), {[Cu(en)₂(H₂O)]₂[Cu(en)₂][α-XCuW₁₁O₃₉]}·5H₂O (3/4, X=Si^IV/Ge^IV), {[Cu(deta)(H₂O)₂]₂[Cu(deta)(H₂O)][α-XCuW₁₁O₃₉]}·5H₂O (5/6, X=Ge^IV/Si^IV) and [Cu(dap)₂]₂{[Cu(dap)₂]₂[Cu(dap)₂][α-PCuW₁₁O₃₉]₂} (7) (en=ethylenediamine, dap=1,2-diaminopropane and deta=diethylenetriamine). 1 is an isolated structure whereas 2 is a 1-D chain structure, but both contain [α-PCuW₁₁O₃₉Cl]⁶⁻ polyoxoanions. 3-6 contain the 1-D linear chains made up of [α-XCuW₁₁O₃₉]⁶⁻ polyoxoanions in the pattern of -A-A-A- (A=[α-XCuW₁₁O₃₉]⁶⁻), while 7 demonstrates the first 1-D zigzag chain constructed from [α-PCuW₁₁O₃₉]₂¹⁰⁻ polyoxoanions via [Cu(en)₂]²⁺ bridges in the pattern of -A-B-A-B- (A=[α-PCuW₁₁O₃₉]₂¹⁰⁻, B=[Cu(en)₂]²⁺). The successful syntheses of 1-7 can provide some experimental evidences that di-/tri-/hexa-vacant polyoxoanions can be transformed into mono-vacant Keggin polyoxoanions under hydrothermal conditions.     

Two new 2-D frameworks based on tetra-copper(II)-substituted sandwich-type polyoxotungstate anions and [Cu2(dien)2(OH)]3+ cations

Two new organic–inorganic polyoxometalates [Cu(dien)(H₂O)]₂{[Cu₂(dien)₂(OH)]₂[Cu₄(B-α-XW₉O₃₃)₂]}·4H₂O (X?=?Sb, 1; X?=?As, 2) (dien?=?diethylenetriamine) were hydrothermally synthesized and characterized by elemental analysis, IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. Both compounds are constructed from one four-coordinate [Cu(dien)(H₂O)]²⁺, one {[Cu₂(dien)₂(OH)]₂[Cu₄(B-α-XW₉O₃₃)₂]} building unit, and four water molecules of crystallization. Structural analysis shows that the sandwich-like polyoxotungstate cluster anions [Cu₄(B-α-XW₉O₃₃)₂]^10? are linked by six adjacent dimeric cations [Cu₂(dien)₂(OH)]³⁺ into a 2-D architecture with a (6,3)-connected topology. Magnetic measurements of 1 and 2 exhibit the presence of antiferromagnetic interactions within the tetranuclear-Cu^II cluster.     

Hydrothermal Synthesis and Structural Characterization of Three One-Dimensional Heteropolytungstates Formed by Mono-CopperII-Substituted Dawson or Keggin Cluster Units

Abstract  Reactions of monovacant Dawson-/Keggin-polyoxoanions, formed in situ from trivacant Dawson-/Keggin-precursors, with copper complexes under hydrothermal conditions lead to three inorganic–organic hybrid polyoxotungstates [Cu(en)₂(H₂O)]₂{[Cu(en)₂(H₂O)]₂[Cu(en)₂]₄[Cu(en)₂][α₂-P₂W₁₇CuO₆₁]₂}·(OH)₂·12H₂O (1), [Cu(dap)₂][Cu(dap)₂(H₂O)]₂[α-PW₁₁CuO₃₉]·(OH)·2H₂O (2) and (H₂en)₂[α-PW₁₁CuO₃₉][Cu(en)₂(H₂O)₂]_0.5·1.5H₂O (3) (en = ethylenediamine and dap = 1,2-diaminopropane). X-ray structural analyses demonstrate that 1 exhibits the first zigzag 1-D chain arrangement constructed from mono-copper^II-substituted Dawson dimeric polyoxoanions [α₂-P₂W₁₇CuO₆₁]₂¹⁶⁻ linked by [Cu(en)₂]²⁺ bridges, whereas 2 and 3 display 1-D linear chain architectures made up of mono-copper^II-substituted Keggin polyoxoanions [α-PCuW₁₁O₃₉]⁵⁻ linked together via corner-sharing MO₆ octahedra (M = Cu or W). Graphical Abstract  Reactions of monovacant Dawson or Keggin polyoxoanions with copper complexes under hydrothermal conditions lead to three novel 1-D chain-like inorganic- organic hybrid polyoxotungstates.      

Syntheses and characterization of two new zinc phosphites with 1D chains decorated by Zn-centered complexes

Two inorganic-organic hybrid solids, Zn₂(phen)(HPO₃)₂ (1) and Zn(phen)(HPO₃) (2), have been synthesized under solvothermal conditions in the presence of 1,10-phenanthroline (phen) ligands. Their structures were determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectra. Compound 1 crystallizes in the triclnic system, space group P-1, , , , α=75.609(1)°, β=79.145(2)°, γ=67.157(2)°, , Z=2. Compound 2 is monoclinic, C2/c, , , , β=94.175(4)°, , Z=8. Both structures consist of 1D chains constructed from strictly alternating ZnO₄ and HPO₃ polyhedra through sharing vertices. The chains are further decorated by Zn-centered complex architectures, [Zn(phen)]²⁺ for 1 and [Zn(phen)₂]²⁺ for 2. The 2D and 3D supramolecular arrays for 1 and 2 are stably stacked via strong π-π interactions of the phen groups, respectively.     

新颖的[Cu~I(dpq)_2]~+配合物阳离子修饰的砷钒酸盐[Cu(dpq)_2]_4[As_8V_(14)O_(42)(H_2O)]·2H_2O的水热合成与结构表征

多金属氧酸盐由于其具有独特的化学结构、特殊的电学、光学和磁学性质以及在催化和医药领域中的应用价值而成为多学科交叉研究的热点课题[1～4].球状的含有低氧化态AsⅢ和VⅣ组分的[As8V14O42(H2O)]4-多阴离子是多金属氧酸盐系列中的一个重要成员,但迄今为止,只有少数此类化合物被报道[5～7].目前,选用新奇的配合物阳离子来修饰多阴离子已被证实是一种构筑具有独特结构的多金属氧酸盐杂化材料的有效方法[8,9].由于dpq(dipyrido[3,2-d:2′,3′-f]quinoxaline,结构见图1)Fig.1Structure of dipyrido[3,2-d:2′,3′-f]quinoxaline(dpq)配体…     

[M(2,2'–bpy)2]2SiW12O40（M=Mn,Co;bpy=联吡啶）的合成、结构及其电催化水产氧性能

用水热法合成了过渡金属联吡啶配阳离子硅钨杂多酸:[M(2,2’-bpy)2]2SiW12O40(M=Mn(1)和M=Co(2)),采用红外光谱、元素分析、热重和单晶X射线衍射对其进行了表征。结果表明,化合物1和2是异质同构体,具有二维格子框架结构。初步研究了2种化合物的电催化H2O析出O2性能,发现化合物1对电催化H2O析出O2有一定的催化作用。     

新颖的[Cu^I（dpq）2]^＋配合物阳离子修饰的砷钒酸盐[Cu（dpq）2]4[As8V14O42（H20）]·2H20的水热合成与结构表征

多金属氧酸盐由于其具有独特的化学结构、特殊的电学、光学和磁学性质以及在催化和医药领域中的应用价值而成为多学科交叉研究的热点课题^[1-4]。球状的含有低氧化态As^Ⅲ和V^Ⅳ组分的[As8V14O42（H20）]^4-多阴离子是多金属氧酸盐系列中的一个重要成员，但迄今为止，只有少数此类化合物被报道^[5-7]。[第一段]     

Hydrothermal Synthesis, Structural Characterization and Properties of Mixed Valent Decavanadium Oxide [Co_2Cl_8V_(10) O_(18)(H_2O)]Cl_2·6H_2O with Novel Three-dimensional Framework

IntroductionPolyoxometalates constitute an enormous classof compounds whose unusual versatility and reac-tivity afford practical applications to many fields,such as catalysis,biology,medicine,and materialsciences[1— 4] .In recent years,hydrothermal tech-nique has become a vital tool in self- assemblychemistry.This technique,in combination with or-ganic templates,has been demonstrated to be wellsuited for the synthesis and the crystal growth ofpolyoxometalates with novel structures[5— 9] .Amo…     

新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

新颖的[CuI(dpq)2]+配合物阳离子修饰的砷钒酸盐[Cu(dpq)2]4[As8V14O42(H2O)]·2H2O的水热合成与结构表征

采用水热方法制备了一个新颖的[CuI(dpq)2]+配合物阳离子修饰的砷钒酸盐[Cu(dpq)2]4[As8V14O42(H2O)]·2H2O, X射线单晶衍射结果表明, 该化合物的结构是由4个[CuI(dpq)2]+阳离子和1个[As8V14O42(H2O)]4-簇阴离子以及2个结晶水组成的, 簇阴离子内部包含一个孤立的水分子.     

Two new hybrid compounds assembled from Keggin-type polyoxometalates and transition metal coordination complexes

Two new hybrid compounds based on Keggin-type polyoxometalates: {[PMo₁₂O₄₀][Ni(Phen)₂(H₂O)]₂}·K·2OH⁻ (1) and [Cd₂(Phen)₄Cl₂][HPW₁₂O₄₀]·H₂O (2) (Phen=1,10-phenanthroline), have been prepared and characterized by IR, UV-vis, XPS, XRD and single crystal X-ray diffraction analyses. Compound 1 exhibits a 1-D chain structure constructed from Pseudo-Keggin polyoxometalate bi-supported transition metal coordination complexes linked by K⁺ ions. Compound 2 contains Pseudo-Keggin polyoxoanions [HPW₁₂O₄₀]²⁻ and novel metal-chloride-ligand coordination complexes [Cd₂(Phen)₄Cl₂]²⁺.     

Hydrothermal Synthesis and Structure Characterization of Open-framework Cobalt-tungsten Phosphate[H3NCH2CH2NH3]3[Co3W4P4O28]

A new three-dimensional open-framework cobalt(Ⅱ)-tungsten(Ⅵ) phosphate,[H3NCH2CH2NH3]3·[Co3W4P4O28](1) has been synthesized from the reaction of CoCl2·6H2O,WO3,H3PO4,ethylenediamine and H2O.The title compound was fully characterized by infrared spectroscopy,elemental analysis,magnetic properties,thermogravimetric analysis,XPS and single-crystal X-ray diffraction.The compound crystallized in a tetragonal space group I4(1)/a with a=1.7118(4) nm,c=1.0773(2) nm,V =3.1568(11) nm3,Z =4.     

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.     

Hydrothermal synthesis and crystal structure of Na(NH4)[C13N2H16]2[Mo7O24]?·?8H2O: A novel 3-D extended supramolecular network with 1-D channels

A novel three-dimensional (3-D) supramolecular assembly of organic bicapped heptamolybdate Na(NH₄)[C₁₃N₂H₁₆]₂[Mo₇O₂₄]·8H₂O has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, and thermogravimetric analysis (TGA). X-ray analyses show that compound 1 represent a novel 3-D extended supramolecular “host” networks with 1-D channels encapsulating flexible cation “guests”. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

新型化合物[Co（en）3]2·2H3O·[As8V4O42（HPO4）]·2H2O晶体的水热合成与表征

近年来，聚氧酸盐化学发展迅速，有些聚氧酸盐作为催化剂已经实现了工业化     

Hydrothermal synthesis and characterization of a new Anderson-type polyoxometalate

A new compound based on Anderson-type polyoxometalate, [Cu(phen)H₂O]₂[CrH₅Mo₆O₂₄]?·5H₂O (1) (phen?=?1,10-phenanthroline), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, and thermal gravimetric analysis. Luminescent, electrochemical, and electroactivity properties of 1 have been studied.     

Hydrothermal syntheses and structural characterization of two sandwich-type arsenotungstates

Two new organic–inorganic composite sandwich-type arsenotungstates [H₂dap]₆H₈[Ni₄(H₂O)₂(B-α-AsW₉O₃₄)₂]₂ · 33H₂O (1) and {[Ni(dap)₂(H₂O)]₂[Ni(dap)₂]₂[Ni₄(Hdap)₂(B-α-AsW₉O₃₄)₂]} · 4H₂O (2) (dap = 1,2-diaminopropane) have been hydrothermally synthesized by reaction of Na₈[A-α-HAsW₉O₃₄] · 11H₂O with NiCl₂ · 6H₂O in the presence of 1,2-diaminopropane and characterized by elemental analysis, IR spectra, X-ray single-crystal diffraction, and thermogravimetric analysis. 1 crystallizes in the triclinic P 1 space group with a = 16.351(6) Å, b = 16.423(6) Å, c = 19.894(7) Å, α = 110.630(6)°, β = 92.684(7)°, γ =104.946(7)°, V = 4774(3) ų, Z = 1, GOOF = 1.033, R ₁ = 0.0517, wR ₂ = 0.1086. 2 also crystallizes in the triclinic P 1 space group with a = 13.305(4) Å, b = 13.882(4) Å, c = 17.031(5) Å, α = 68.109(5)°, β = 71.511(4)°, γ = 88.407(5)°, V = 2753.5(14) ų, Z = 1, GOOF = 1.051, R ₁ = 0.0491, wR ₂ = 0.1150. Notably, 1 is a discrete structure, composed of two tetra-Ni^II substituted sandwich-type polyoxoanions [Ni₄(H₂O)₂(B-α-AsW₉O₃₄)₂]^10? with different spatial orientation, whereas 2 displays a organic–inorganic composite 2-D sheet architecture constructed by tetra-Ni^II sandwiched [Ni₄(H₂O)₂(B-α-AsW₉O₃₄)₂]^10? units by means of [Ni(dap)₂]²⁺ bridges. Some previously reported transition-metal-substituted sandwich-type polyoxotungstates have been summarized.     

A novel zigzag chain based on polyoxomolybdate decorated by glycine ligand in covalent bond

An unusual compound, K₂[Mo₄O₁₃(NH₃CH₂COO)₂]?·?2H₂O (1), has been synthesized and structurally characterized by the XRD, elemental analysis, IR spectrum, TG analyses and the single crystal X-ray diffraction. The structure of 1 exhibits a zigzag chain based on corner-shared tetramolybdate chelated by two bidentate glycine ligands.     

A novel 2D layer structure constructed from sandwich-type transition metal substituted tungstates and nickel coordination fragments: {[Ni(enMe)2]2[Ni(enMe)2(H2O)]2[As2W18Ni4(enMe)2O68]}·2H3O·2H2O

A novel polyoxometalate {[Ni(enMe)₂]₂[Ni(enMe)₂(H₂O)]₂[As₂W₁₈Ni₄(enMe)₂O₆₈]}·2H₃O·2H₂O (1) (enMe = 1,2-propylenediamine) has been synthesized and characterized, which is the first high-dimensional structure constructed from sandwich-type transition metal substituted tungstates and transition metal coordination groups.