铜配合物修饰的Dawson型钨磷酸盐的合成、晶体结构和催化性能

在水热条件下,Cu(Ⅱ)-H₂biim配合物与Dawson型钨磷酸盐构筑了1个无机-有机杂化化合物[Cu(H₂biim)₂(H₂O)][{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]·11H₂O(1)(H₂biim=2,2'-联咪唑)。 通过单晶X射线衍射、红外光谱(IR)、X射线粉末衍射(XRD)、元素分析、电化学分析等技术手段对其进行了表征。 结构分析表明,在化合物1分子中,[P₂W₁₈O₆₂]^6-单元作为双齿配体与2个Cu²⁺离子配位形成双支撑的杂多阴离子[{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]^2-,在其外部有1个游离的[Cu(H₂biim)₂(H₂O)]²⁺ 和11个H₂O分子。 H₂biim分子与杂多阴离子/H₂O分子间存在氢键,通过氢键、静电和π-π堆积作用,进一步构成具有3D结构的晶体材料。 该晶体化合物对H₂O₂和NaNO₂的还原具有良好的电催化作用;同时,作为酸催化剂用于合成环己酮乙二醇缩酮反应,催化活性高,可重复使用。     

两个基于八钼酸盐的无机-有机杂化材料的合成、结构和光催化性能

通过水热法成功合成了两个新的基于(β-Mo₈O₂₆)^4-构型的无机-有机杂化材料,分子式分别为{[Ni(β-Mo₈O₂₆)(H₂O)₄](H₂Fbix) 2H₂O}_n(1)和{[Co(β-Mo₈O₂₆)(H₂O)₄](H₂Fbix) 2H₂O}_n(2)(Fbix=2,3,5,6-四氟-二(1,4-咪唑-1-甲基)苯)。利用X-射线单晶衍射、X-射线粉末衍射、红外光谱、热重分析和元素分析等对该化合物的结构和性能进行了表征。晶体结构分析表明：化合物1和2为同构化合物。在化合物1中,扭曲八面体构型的Ni^II与两个β-[Mo₈O₂₆]^4-单...     

基于柔性四羧酸的三个一维/二维/三维Zn(Ⅱ)/Co(Ⅱ)配合物的晶体结构及荧光性质

通过水热/溶剂热合成的方法制备了3个Zn(Ⅱ)/Co(Ⅱ)配合物{[Zn(H₂L)(H₂O)₃]·H₂O·0.5H₄L}_n(1)、{[Co(L)_0.5(4,4'-bpy)]·0.5H₂O}_n(2)和{[Co(L)_0.5(pbmb)(H₂O)]·H₂O}_n(3)(H₄L=5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid,4,4'-bpy=4,4'-bipyridine,pbmb=1,1'-(1,3-propane)bis-(2-methylbenzimidazole))。结构分析表明配合物1为一维链结构。2为拓扑符号为(6⁴·7·8)(6·7²)的三重穿插网络结构。3是拓扑符号为(4·6²)(4²·6²·8²)的(3,4)-连接的二维网络结构。配合物1呈现出较好的荧光性质。     

水合铵硼氧酸盐及其饱和溶液的FTIR和Raman光谱研究

研究了NH₄B₅O₈·4H₂O和(NH₄)₂B₈O₁₃·6H₂O及其饱和溶液于20℃的FTIR和Raman光谱,对振动频率进行了归属.根据振动光谱特征,预测(NH₄)₂B₈O₁₃·6H₂O中所含基本结构单元为[B₇O ₁₁(OH)·B(OH)₃]^2-.首次将Raman光谱中516cm^-1处的强散射峰归属为这一多聚硼氧配阴离子的对称脉冲振动峰,并对以上2种铵硼氧酸盐饱和溶液中硼氧配阴离子的存在形式{B(OH)₃,[B₃O₃(OH)₄]^-和[B₅O₆(OH)₄]^-}和相互作用机理进行了探讨.     

基于Keggin型杂多酸的无机-有机杂化物的合成和光催化活性

采用水热合成方法制备了2个基于Keggin型杂多酸的无机-有机杂化物, 化学式分别为{[Cu₂(4,4′- bipy)₄(H₂O)₄](SiMo₁₂O₄₀)·18H₂O}_n(1)和{[Cu₂(4,4′-bipy)₄(H₂O)₄](PMo₆W₆O₄₀)·18H₂O}_n(2)(bipy=bipyridine). 结构分析 表明2个化合物同构, Cu²⁺是六配位, 分别与4个4,4′-bipy上的N原子和2个水分子上的O原子结合, 形成 [Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺二维层状结构. 杂多阴离子通过静电与配位阳离子[Cu(4,4′-bipy)₂(H₂O)₂]_n²ⁿ⁺作用交叉排列在层间. 通过红外光谱、 粉末X射线衍射和固体紫外-可见漫反射光谱等对化合物的性质进行了表征. 研究了所合成化合物对水溶性染料亚甲基蓝的降解活性, 发现2种化合物对于亚甲基蓝均表现出显著的光降解活性, 并对它们的催化机理进行了讨论.     

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.     

过渡金属-联咪唑-Dawson型钨磷酸盐杂化化合物的酶固定化性能

利用水热法和直接沉淀法, 设计合成了5例由过渡金属(TM)-联咪唑配阳离子与Dawson型钨磷酸阴离子构成的多金属氧酸盐(POM)基有机-无机杂化化合物[Ni(H₂biim)₃]₄[Ni(H₂biim)₂(P₂W₁₈O₆₂)₂]·2H₂O(1), [Co^III(H₂biim)₃]₂[P₂W₁₈O₆₂]·8H₂O(2), [Cu(H₂biim)₂]₃[P₂W₁₈O₆₂]·4H₂O(3), [Co^II(H₂biim)₃]₂H₂[P₂W₁₈O₆₂]·9H₂O(4)和 [Ni(H₂biim)₃]₃[P₂W₁₈O₆₂]·2H₂O(5); 并利用X射线单晶衍射分析(SC-XRD)、 红外光谱(IR)和热重-差热分析 (TG-DTA)等对其进行了表征. 化合物1~5作为载体用于固定辣根过氧化物酶(HRP)时, 显示出了较高的酶固定化能力. 另外, 利用圆二色光谱(CD)和激光扫描共聚焦显微镜(LSCM)等方法评价了固定化酶HRP/1~HRP/5的重复使用性、 储存稳定性和检测过氧化氢(H₂O₂)的性能. 由于该类POMs与HRP间存在强的相互作用, 利用简单的物理吸附法即可实现POMs对HRP的固载. POMs对酶的固定不但提高了HRP对使用及储存环境的耐受性, 同时也拓展了POMs在酶固定化领域的应用.     

一个基于[Cu4(μ2-OH)2N12]的10-连接3D配合物的合成、结构和光催化性质

通过扩散法合成了一个新的配位聚合物{[Cu₂（OH）（btre）_1.5（1,2,4-btc）]·13H₂O}_n（1·13H₂O）（btre=1,2-二（4H-1,2,4-三唑）乙烷,1,2,4-btc=1,2,4-苯三甲酸根）。测试了1·13H₂O的晶体结构,并用红外光谱、元素分析、粉末X射线衍射对其进行表征。单晶X射线衍射表明1是基于四核铜簇[Cu₄（μ₂-OH）₂N₁₂]构筑的10-连接的3D框架,其拓扑符号为3¹²·4²⁸·5⁵。研究了1·13H₂O的热稳定性以及对甲基橙的催化降解作用。     

一种基于2,6-双(1,2,4-三唑-1-基)吡啶的新型多酸基无机-有机杂化材料的合成、结构与质子导电性能研究

采用水热法合成了一种新型多酸基无机-有机杂化材料{[Co(btp)(Hbtp)(H₂O)₃](PW₁₂O₄₀)·3H₂O}_n(1),并对化合物1进行了结构测定。X射线单晶衍射结果显示，Co(Ⅱ)离子通过btp配体连接形成一维链，[PW₁₂O₄₀]^3-游离于相邻一维链相互交叉形成的孔隙中，从而扩展成三维结构。热重分析表明化合物1具有良好的热稳定性。此外，还对化合物1的质子导电性能进行了研究。结果表明，化合物1在358 K和98%RH条件下的质子电导率为6×10^-5 S·cm^-1。     

HEDP与Fe(Ⅲ)配位化合物的制备和性质研究

制备了K₃[Fe(C₂H₅P₂O₇)₂]·4.5H₂O和K₃[Fe(C₂H₆P₂O₇)₂(OH)₂]·3H₂O两种固体配合物,用化学分析、穆斯堡尔谱、红外光谱、差热热重分析和电导测定等研究了它们的性质,推测了配合物的结构。     

A unique borotungstate containing a discrete Keggin-type anion and a trimeric saturated Keggin-type anion

A unique hybrid borotungstate, [Cu(En)(Phen)(H₂O)]₄[α-BW₁₂O₄₀]{[Cu(En)(Phen)]₂[Cu(En)₂ · (H₂O)]₂[Cu(En)(Phen)(H₂O)]₂[α-BW₁₂O₄₀]₃]} sd 10H₂O (I) (Phen = 1,10-phenanthroline, En = ethylenediamine), has been hydrothermally synthesized and characterized by elemental analyses, IR, and UV spectra, powder X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, and singlecrystal X-ray diffraction analysis. X-ray crystallography shows that I contains a discrete saturated Keggin-type [BW₁₂O₄₀]⁵⁻ polyoxoanion and a rare trimeric saturated Keggin-type polyoxoanion {[Cu(En)(Phen)]₂[Cu(En)₂(H₂O)]₂[Cu(En)(Phen)(H₂O)]₂[α-BW₁₂O₄₀]₃]}³⁻. It is noteworthy that I represents the first example of borotungstate containing four saturated Keggin-type units in one molecule.     

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.     

Two New 2D and 1D Ni(II) Coordination Polymers Bridged by Vanadium-Substituted Keggin Polyoxotungstophosphates: Hydrothermal Synthesis and Crystal Structure

Two coordination polymers based on vanadium-substituted Keggin polyoxotungstophosphates as bridging ligands, {[Ni(4,4′-bipy)_1.5(OH)(H₂O)]₂[H₃PW₁₀V₂O₄₀]}·4H₂O (4,4′-bpy = 4,4′-bipyridine) 1 and {[Ni(dpa)₂][Ni(dpa)(H₂O)₃]₂[PW₉V₃O₄₀]}·4H₂O (dpa = 2,2′-dipyridylamine) 2, have been obtained by hydrothermal reactions and characterized by elemental analysis, IR, XRD, TGA and single-crystal X-ray Diffraction analysis. Compound 1 is a 2D layered structure built from 1D infinite zigzag {Ni₂(4,4′-bipy)₃(OH)₂(H₂O)₂}_n²⁺ chains bridged via [H₃PW₁₀V₂O₄₀]²⁻ anions. Compound 2 exhibits a one-dimensional chain-like structure constructed from [Ni(dpa)₂]²⁺ fragments bridged via bis-supported Keggin polyoxoanions [Ni(dpa)(H₂O)₃]₂[PW₉V₃O₄₀]²⁻. The two examples demonstrate that vanadium-substituted Keggin polyoxometalates have greater coordination capability.     

Organic-inorganic hybrids constructed by Anderson-type polyoxoanions and copper coordination complexes

Four organic-inorganic hybrid compounds based on Anderson-type polyoxoanions, namely, {[Cu(2,2′-bpy)(H₂O)₃]₂[Cr(OH)₆Mo₆O₁₈]}{[Cu(2,2′-bpy)(H₂O)Cl][Cu(2,2′-bpy)(H₂O)(NO₃)][Cr(OH)₆Mo₆O₁₈]}·18H₂O (1), [Cu(2,2′-bpy)(H₂O)₂Cl]{[Cu(2,2′-bpy)(H₂O)₂][Cr(OH)₆Mo₆O₁₈]}·4H₂O (2), (H₃O){[Cu(2,2′-bpy)(H₂O)₂]₂[Cu(2,2′-bpy)(H₂O)]₂}[Cr(OH)₆Mo₆O₁₈]₃·36H₂O (3), and (H₃O){[Cu(2,2′-bpy)(H₂O)₂]₂[Cu(2,2′-bpy)(H₂O)]₂}[Al(OH)₆Mo₆O₁₈]₃·33H₂O (4), were isolated by conventional solution method, and crystal structures have been determined by single-crystal X-ray diffraction. Among them, compound 1 displays a discrete supramolecular structure, compound 2 shows a chainlike structure with chloro-copper complexes as counteranions, and compounds 3 and 4 are isomorphic and exhibit unique 3D open frameworks with lattice water molecules residing in the channels. The compounds 3 and 4 represent the first example of 3D organic-inorganic hybrid compounds in the TMs/2,2′-bpy/POMs system. Investigation of the reaction conditions reveals that the geometry and size of the anions together with its coordinating abilities to the metal centers have a decisive influence on both the composition and the dimensionality of the final compounds.     

Hydrothermal Syntheses and Crystal Structures of Two New Heteropolyoxovanadoborates Containing {(VO)<Subscript>12</Subscript>O<Subscript>6</Subscript>[B<Subscript>3</Subscript>O<Subscript>6</Subscript>(OH)]<Subscript>6</Subscript>(H<Subscript>2</Subscript>O)} Cluster

Two new heteropolyoxovanadoborates (H₂dap)₂H₆{(VO)₁₂O₆[B₃O₆(OH)]₆(H₂O)}·13H₂O (1, dap = 1,2-diaminopropane) and {[Zn(dien)]₂[Zn(dien)(H₂O)]₄(VO)₁₂O₆[B₃O₆(OH)]₆(H₂O)}₂·15H₂O (2, dien = diethylenetriamine) have been hydrothermally synthesized and structurally characterized. Both 1 and 2 contain {(VO)₁₂O₆[B₃O₆(OH)]₆(H₂O)} cluster (denoted on V₁₂B₁₈), which is constructed by a puckered B₁₈O₃₆(OH)₆ ring sandwiched between two triangles of six alternating cis and trans edge-sharing vanadium atoms, and a central water molecule. 1 consists of discrete [V₁₂B₁₈]¹⁰⁻ cluster anions with H₂dap²⁺ as counterions, while 2 consists of discrete neutral {[Zn(dien)]₂[Zn(dien)(H₂O)]₄[V₁₂B₁₈]} clusters, which are built from two types of zinc(II) complex fragments connecting with V₁₂B₁₈ cluster through two Zn-(μ ₃-O)-B bonds. Interestingly, 2 is the only example of the V₁₂B₁₈ cluster decorated by two types of zinc(II) complex fragments.     

Studies of Copper(II) Thiosemicarbazide Complexes and their Reactivities. X-Ray Structure of Two Unusual Reaction Products, [Cu(bpy)(H2O)2SO4] and [(bpy)2Cu2(C2O4)Cl2]·H2O

A number of ternary complexes of Cu²⁺ with thiosemicarbazide (TSC) including [Cu(bpy)(TSC)₂]Cl₂, [Cu(o-phen)(TSC)₂]Cl₂ and [Cu(bpy)(TSC)₂][CuCl₄] [Cu(o-phen)(TSC)₂] [CuCl₄] have been synthesised and characterized. Their reactivities in aqueous and DMF solutions were studied. It was observed that while on coordination to Cu²⁺ thiosemicarbazide is converted to thiocyanate in aqueous solution, in DMF solution the thiocyanate is further aerially oxidised to sulfate. In the presence of hydrogen peroxide, oxidation to sulfate is rapid and from the mother liquor we could isolate [(bpy)₂Cu₂(C₂O₄)Cl₂]·H₂O whose structure was determined by X-ray crystallography. X-ray crystal structure of [Cu(bpy)(H₂O)₂SO₄] is also discussed.*     

Two compounds constructed from Strandberg-type polyoxoanions,metals and organic ligands

Two new hybrid compounds, [Cu(1)(phen)(H₂O)][Cu(2)(phen)(H₂O)]([Cu(3)]_0.25(H₂O)][P₂Mo₅O₂₃]·3.75H₂O (1) and [Cu(en)₂]_1.5[P₂Mo₅O₂₃]₂·(enH₂)₃·2H₂O (2) (phen = 1,10-phenanthroline, en = ethylenediamine), have been hydrothermally synthesized and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, TG analyses, cyclic voltammogram analyses, elemental analyses, and single crystal X-ray diffraction analyses. Single crystal X-ray diffraction analyses reveal that the two compounds have a 1-D chain structure formed by Strandberg-type POMs and TMCs with –A–B–C–B–A–B–C–B– linking mode, then further extend into a 2-D layer structure through π?π or hydrogen bond interactions.     

Assembly of three supramolecular compounds based on [P2Mo5O23]6− and Ni(II) complexes

Three supramolecular compounds based on [P₂Mo₅O₂₃]^6? and Ni(II)–bim, [Ni(bim)₃]₃[P₂Mo₅O₂₃]·2H₂O (1), [Ni(Hbim)(bim)₂]₄[P₂Mo₅O₂₃]₂·3H₂O (2), and [Ni(bim)(Hbim)(phen)]₂[P₂Mo₅O₂₃]·7H₂O (3) (bim?=?2,2′-biimidazole, phen?=?1,10-phenanthroline), have been synthesized under hydrothermal conditions and characterized by elemental analysis, single-crystal X-ray diffraction, IR, and TG. All the compounds show 3-D supramolecular networks constructed from weak interactions among free Ni(II) complex, water, and oxygens of [P₂Mo₅O₂₃]^6?. Compound 3 represents the first supramolecular example integrating {Ni(bim)(Hbim)(phen)} with Strandberg-type phosphomolybdate. The compounds display good electrocatalytic activity to reduce hydrogen peroxide and intense fluorescence properties in solution at room temperature.     

Synthesis and crystal structures of supramolecular adducts of molybdenum and tungsten selenide aqua complexes with macrocyclic cavitand cucurbituril

The supramolecular compounds {[W₃Se₄Cl₃(H₂O)₆]₂[PyHC₃₆H₃₆N₂₄O₁₂]}Cl₃·18H₂O (1) and {[Cl₃SnMo₃Se₄Cl₃(H₂O)₆][Cl₃SnMo₃Se₄Cl₂(H₂O)₇](C₃₆H₃₆N₂₄O₁₂)}Cl·26H₂O (2) were isolated from solutions of the selenium-containing tungsten and molybdenum clusters [W₃Se₄(H₂O)₉]⁴⁺ and [Cl₃SnMo₃Se₄(H₂O)₉]³⁺, respectively, and organic cavitand cucurbituril. X-ray diffraction analysis demonstrated that the macrocylcic cucurbituril molecule is coordinated on both sides by the cluster cations through the formation of complementary hydrogen bonds. Compound 1 has a chain structure stabilized by Se...Se interactions between the adjacent cluster cores. In compound 2, the bridging ₂-selenium atoms of the cluster fragment Mo₃Se₄ are coordinated to the tin atom of the SnCl₃ ^– ligand, thus losing the ability to be involved in Se...Se interactions.     

Synthesis,spectral and structural studies of a Mn(II) complex of [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic acid ethyl ester and Mn(II) and Ni(II) complexes of [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic acid methyl ester

The new complexes [Mn(Hpchce)₂(o-phen)], {2[Mn(pchcm)(o-phen)₂]}·7H₂O and [Ni(Hpchcm)(o-phen)₂]Cl·CH₃OH with [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic acid ethyl ester (H₂pchce) and [N′-(pyridine-4-carbonyl)-hydrazine]-carbodithioic acid methyl ester (H₂pchcm) have been synthesized, containing o-phenanthroline (o-phen) as a coligand. These ligands and their complexes have been characterized by elemental analyses, IR, magnetic susceptibility and single crystal X-ray data. H₂pchce (2), [Mn(Hpchce)₂(o-phen)] (3) {2[Mn(pchcm)(o-phen)₂]}·7H₂O (4) and [Ni(Hpchcm)(o-phen)₂]Cl·CH₃OH (5) crystallized in the monoclinic system, space group Pc, C2/c, P21/n and P21/n, respectively. The (N, O) donor sites of the bidentate ligands chelate the Mn(II) and Ni(II) centers forming a five-membered CN₂OM ring. The resulting complexes are paramagnetic and have a distorted octahedral geometry.