Two 2D inorganic–organic hybrid materials constructed from (V2O6)n2n− chains linked through metal–organic units [Cd(ip)]/[Ni(ip)(H2O)]

Two novel inorganic–organic hybrids [Cd(ip)V₂O₆] (1) and [{Ni(H₂O)(ip)}V₂O₆ ]·H₂O (2) {ip = imidazo[4,5-f ][1,10]-phenanthroline} have been prepared and characterized by single crystal X-ray diffraction, IR and TG. Two-dimensional frameworks of the two title compounds are constructed from arrays of (V₂O₆)_n^2n? oxovanadate chains covalently linked through metal–organic units, {Cd(ip)} and {Ni(ip)(H₂O)}. The {M/V/O/N} layers are composed of corner sharing {VO₄} tetrahedra and {MN₂O₄} octahedra. In compound 1, the cadmium ions are bridged alternately by two μ₃-O and two VO₄ units, generating alternated four-membered Cd₂O₂ and eight-membered Cd₂V₂O₄ rings, while the nickel ions of compound 2 are linked simultaneously by VO₄ and V₃O₁₀ units into twelve-membered Ni₂V₄O₆ ring. The ip groups, bonded to the metal centers in the layers, project outward to occupy regions in between the successive metal oxide layers. Furthermore, the adjacent layers [Cd(ip)V₂O₆]_n in compound 1 are linked with each other by hydrogen bonding to generate an interesting 3D supramolecular framework.     

配合物[Co(phendione)(SO4)(H2O)]5H2O非等温热分解动力学

以热重-差热法(TG-DTG)为手段,研究配合物[Co(phendione)(SO4)(H2O)]·5H2O非等温热分解过程动力学.结果表明,标题配合物第一阶段热分解为相界控制反应(三维)机理,表观活化能为59.85KJ·mol-1,指前因子InA为16.36,反应速率方程为dα/dt=Ae-E(1-α)<2/3>.第...     

Two novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu2Ln2(ox)(SiW11)2} dimers and [Cu(en)(ox)]/[Cu(en)2] linkers

Two novel 2-D organic–inorganic hybrid silicotungstates [H₂en][Cu(en)₂(H₂O)]₂{[Cu(en)₂]₃[Cu(en)(ox)]₂[Ln₂(ox)(α-SiW₁₁O₃₉)₂]}·nH₂O (Ln = Er^III, n = 10 for 1, Ln = Sm^III, n = 8 for 2) with mixed organic ligands of ox and en (ox = oxalate, en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectrum, thermogravimetric analysis (TGA), power X-ray diffraction (PXRD) and X-ray single-crystal diffraction, respectively. Notably, 1 and 2 are isomorphic and exhibit the first novel 2D organic–inorganic hybrid silicotungstates assembled by {Cu₂Ln₂(ox)(SiW₁₁)₂} dimers and [Cu(en)(ox)]/[Cu(en)₂] linkers. Furthermore, the TG curve of 1 and 2 display three steps of weight loss in the range of 25–1000 °C.     

化合物[Co(2,2'-bpy)2H2O]12[Mo12V6O42(VO4)][Mo8V8O40(VO4)]3·8H2O的水热合成与晶体结构

用中温水热法合成出一种新的α-Keggin结构化合物[Co(2,2'-bpy)2H2O]12[Mo12V6O42(VO4)][Mo8V8O40(VO4)]3·8H2O,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.该簇合物属三斜晶系,空间群P-1,a=1.57287(2)nm,b=2.46159(3)nm,c=0.52347(3)nm,α=76.6220(3)°,β=92.078°,γ=79.9390(4) °,V=9.1934(2)nm3,Z=2,Dc=4.642 g·cm-3,μ=4.642mm-1,F(000)=12420,R1=0.0751,wR2=0.1964.化合物中基本构筑单元为三种具有α-Keggin结构的聚阴离子簇,簇与簇之间通过配位阳离子[Co(2,2'-bpy)2H2O]2+桥连成三维结构.化合物中包含少见的六帽α-Keggin结构簇单元.并且在同一晶胞中同时存在聚阳离子和聚阴离子.     

配位聚合物{[Zn(L)(CH_3COO)]·(H_2O)}_n的合成及结构表征

本文在水热条件下合成了一个基于双功能配体4-(2-苯并咪唑基)苯甲酸(L)和Zn(Ⅱ)的配位聚合物{[Zn(L)(CH_3COO)]·(H_2O)}n(1),并通过红外及X-射线单晶衍射表征了该化合物的结构。该化合物的晶体属单斜晶系,P2(1)/c空间群,晶胞参数如下:a=17.3443(9)?,b=10.2451(5)?,c=8.3316(5)?,β=100.320(5)°,V=1456.53(13)?~3,Z=4,Dc=1.731 mg/m~3,R1=0.0714。配位聚合物1表现为2D结构,中心离子锌为四配位的扭曲四面体构型。     

[Co(Ⅱ)(H2O)6](C4H4O4)·2C6H12N4·4H2O修饰电极电化学催化谷胱苷肽研究

利用气相沉积法研制了基于TiO2凝胶固定化[Co(H2O)6](C4H4O4).2C6H12N4.4H2O(CoL)修饰电极。研究了该修饰电极对谷胱苷肽(GSH)的催化活性,发现在pH 7.5,0.1 mol/L NaAc-HAc的缓冲溶液中,CoL对电氧化GSH浓度之间有较好的线性关系.线性范围为2×10-6~1×10-4mol/L,检测下限为8×10-7mol/L,相对标准偏差为2.0%(cGSH=5×10-6mol/L,n=6)。应用该法测定生物样品中谷胱苷肽的含量并与紫外分光光度法进行对照,结果一致。     

Synthesis,structural characterization and properties of a novel 1D helical chain arsenomolybdate {[Cu(en)2][Cu(en)(H2O)][(Cu(en)2(H2O)] [AsIIIAsVMo9O34)]} · 2H2O

An organic–inorganic hybrid 1D helical chain arsenomolybdate {[Cu(en)₂][Cu(en)(H₂O)][(Cu(en)₂(H₂O)] [As^IIIAs^VMo₉O₃₄)]} · 2H₂O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by elemental analyses, IR, UV and CD spectrum, powder X-ray diffraction, TG-DTA and single-crystal X-ray diffraction. The asymmetric unit of 1 consists of a monocapped trivacant Keggin [As^IIIAs^VMo₉O₃₄]^6 − subunit, a pendant [Cu(en)₂(H₂O)]^2 + cation, a pendant [Cu(en)(H₂O)]^2 + cation, one bridging [Cu(en)₂]^2 + cation and two lattice water molecules. It should be noted that 1 illustrates a one-dimensional (1D) helical chain assembled by {[Cu(en)(H₂O)][(Cu(en)₂(H₂O)][As^IIIAs^VMo₉O₃₄)]}^2 − clusters and [Cu(en)₂]^2 + linkers.     

新型配位聚合物[Co(C5H5N)2(H2O)2(O2CC2H4CO2)]n的水热合成和晶体结构

以CoCl2.6 H2O和丁二酸(CH2COOH)2、三乙胺为原料,在中温水热反应条件下,合成了一种新型配位聚合物[Co(C5H5N)2(H2O)2(O2CC2H4CO2)]n,并对其进行了X射线单晶衍射和红外光谱测定。晶体数据如下:正交晶系,Pbca空间群,a=11.91940(12)nm;b=8.91440(10)nm;c=15.1025(2)nm;α=90.00;β=90.00;γ=90.00;V=1604.71(3)nm3;Z=4;Dc=1.528 g/cm3;μ=1.101 mm-1;F(000)=764;R1=0.0492,wR2=0.0831。该晶体通过分子间氢键和相互作用的π-π键形成一维的链状结构。     

{[Zn(hmph)(bped)_(0.5)(H_2O)](H_2O)}_n的合成及晶体结构研究

以邻羧基苯乙酸和内消旋-1,2-双(4-吡啶)-1,2-乙二醇为有机配体,合成了一个新的Zn(II)配位聚合物{[Zn(hmph)(bped)0.5(H2O)](H2O)}n,并对其晶体结构进行了研究。该晶体属于三斜晶系,p-1空间群,晶胞参数a=7.6732(4),b=8.3888(3),c=13.3689(6),α=97.091(3)°,β=98.672(4)°,γ=111.061(4)°,V=779.02(6)3,Z=2,Dc=1.653 mg/m3,最终偏差因子R1=0.0359,wR2=0.0852[I"2#(I)],F(000)=398.0。该配合物为1D链结构,通过氢键堆积为最终的3D框架。     

First transition metal coordination compound supported on metal–oxygen cluster with bicapped quasi-Keggin structure: [Cu(en)2(H2O)]4[Cu(en)2]3.5[PMoVI8VIV6O42Cu(en)(1,10′-phen)]3·14H2O

A novel compound, [Cu(en)₂(H₂O)]₄[Cu(en)₂]_3.5[PMo^VI₈V^IV₆O₄₂Cu(en)(1,10^′-phen)]₃·14H₂O 1 (en = ethylenediamine, phen = phenanthroline), was synthesized hydrothermally (170 °C, 10 days, autogeneous pressure) and characterized by IR, ESR, elemental analyses and X-ray crystallography. The results of structure determination show that compound 1 contains three different structure cluster anions [PMo^VI₈V^IV₆O₄₂]⁷⁻ supporting complex cation [Cu(en)(1,10^′-phen)]²⁺, in which one cluster anion possesses typical bicapped Keggin structure, while other two polyanions only have bicapped quasi-Keggin structures, and [Cu(en)(1,10^′-phen)]²⁺ is linked through oxygen atoms to different V positions of two bicapped quasi-Keggin units.     

An unexpected 3D (6, 8)-connected metal–organic framework {[Cu5(trz)2(mal)2(fma)(H2O)4]·2H2O}n: Synthesis,structure and catalytic thermodecomposition for ammonium perchlorate

A crystalline 3D MOF {[Cu₅(trz)₂(mal)₂(fma)(H₂O)₄]·2H₂O}_n (1) (trz = 1,2,4-triazolate, mal = malate, fma = fumarate) has been synthesized through hydrothermal method and characterized by X-ray crystallography, IR, elemental analysis and thermal gravimetric analysis. The crystal structure revealed that the fma was partly in situ converted into the mal under hydrothermal conditions and the compound was consisted of a 3D (6, 8)-connected honeycomb-like network. Furthermore, the catalytic performance of compound for the thermal decomposition of ammonium perchlorate (AP) was investigated by DSC. The experiment results indicated that the compound accelerated the decomposition of AP.     

Two inorganic–organic hybrid compounds based on [Ni2(V3O9)2]2− cluster and {Co2V2} cage subunits

Two novel inorganic-organic hybrid compounds (Ni₃(Hfcz)₄(V₃O₉)₂? 2H₂O) (1) and Co₅(H₂O)₄(fcz)₂(V₄O₁₂)₂ (2) have been successfully constructed, based on [Ni₂(V₃O₉)₂]^2? “bow tie” clusters and {Co₂V₂} pure inorganic cages. Structural analysis reveals that the clusters and cages are expanded to a 2D network and 3D framework via Ni^II and Co^II, respectively. In addition, we investigated the optical band gaps of the two compounds: 2.92 eV and 2.23 eV.     

Single crystal structure of a two-dimensional framework: [{Co(4,4′-bpy)(HO3PCH2CH2CH2CH2PO3H)(H2O)2}·4H2O]n

The structure of [{Co(4,4^′-bpy)(HO₃PCH₂CH₂CH₂CH₂PO₃H)(H₂O)₂}·4H₂O]_n 1 was determined by single crystal X-ray diffraction. Compound 1 contains a new two-dimensional framework layer, which is built up from parallelogram units in bc plane. The layers are constructed into a three-dimensional structure by interlayer hydrogen bonds.     

A 2-D polymer constructed through bridging acetate,hydroxo, aqua and bipyridine ligands: crystal structure of {[Cu2(μ-CH3COO)(μ-OH)(μ-H2O)(4,4′-bipy)](2H2O)(SiF6)}n

A novel 2-D coordination polymer constructed by μ₂-acetate-O,O^′, μ₂-hydroxo, μ₂-aqua and 4,4^′-bipyridine (bipy) ligands has been synthesized and structurally characterized. Linear 1-D chain built by bridged μ₂-acetate-O,O^′, μ₂-hydroxo and μ₂-aqua units is composed of Cu₂O₂ motifs and syn-anti bridged acetate ligands. The copper atom with a five-coordination has a distorted square-pyramidal geometry completed by two nitrogen atoms from 4,4^′-bipyridine and three oxygen atoms from acetate, hydroxo and water ligands. The strong stacking effect is observed between 4,4^′-bipyridine ligands.     

An organic–inorganic hybrid 1-D double-chain copper–yttrium heterometallic silicotungstate [Cu(dap)2(H2O)]2{Cu(dap)2[α-H2SiW11O39Y(H2O)2]2}·10H2O

An organic–inorganic hybrid 1-D double-chain Cu^II–Y^III heterometallic silicotungstate [Cu(dap)₂(H₂O)]₂ {Cu(dap)₂[α-H₂SiW₁₁O₃₉Y(H₂O)₂]₂}·10H₂O (1) has been synthesized by reaction of Na₁₀[A-α-SiW₉O₃₄]·18H₂O, CuCl₂·2H₂O, YCl₃ and dap (dap = 1,2-diaminopropane) under hydrothermal conditions and characterized by elemental analyses, IR spectrum, UV spectrum and single-crystal X-ray diffraction. 1 exhibits a novel 1-D double-chain structure constructed from dimeric Cu^II–Y^III heterometallic silicotungstate units. To our knowledge, 1 is the first organic–inorganic hybrid 1-D double-chain Cu^II–Y^III heterometallic polyoxometalate. Thermogravimetry-differential thermal analysis of 1 has been measured from 25 to 750 °C and the thermogravimetric curve indicates two steps of weight loss.