新型四核铜配合物{[Cu4L2（N3）2（μ2-N3）2]·CH3OH}的合成及其晶体结构

多吡啶配体H2L[N,N’-二(3-甲基吡啶基)-2,6-吡啶二酰胺]与Cu(OAc)2.H2O反应合成了一种新型的四核铜配合物——[Cu4L2(N3)2(μ2-N3)2].CH3OH(1),其结构经IR,XRD和元素分析表征。1属单斜晶系,空间群C2/m,晶胞参数a=15.774(3),b=15.062(3),c=10.724(2),β=114.91(3)°,V=2 344.0(8)3,Z=4,Dc=1.736 mg.cm-3,μ=1.869 mm-1,R1=0.120 1,ωR2=0.298 4。1中四个金属铜原子通过两个L2-配体,四个N3-基团连接在一起,形成了一个新颖的四核铜结构。     

新型单核Ni（Ⅱ）配合物{[Ni（phen）（H2O）4]·（1,5-nds）·H2O}的合成及其晶体结构

以1,5-萘二磺酸钠和1,10-邻菲罗啉为配体,Ni(Ⅱ)为中心离子,采用蒸发溶剂法,在去离子水中合成了一个新型的单核Ni(Ⅱ)配合物{[Ni(phen)(H2O)4]·(1,5-nds)·H2O(1),phen=1,10-邻菲罗啉,1,5-nds=1,5-萘二磺酸根离子},其结构经IR,元素分析和X-射线单晶衍射表征。1属单斜晶系,空间群C2/c,晶胞参数a=20.590 9(18),b=12.435 0(11),c=12.539 0(12),β=124.652(2)°,Z=4,V=2 641.1(4)3。在1的分子结构中,中心离子Ni(Ⅱ)与phen和四个水分子配位,呈八面体构型;1,5-nds没有配位,起平衡电荷作用。     

三维穴状化合物[Zn3（pda）2（SO4）（H2O）4·4H2O]的合成与表征

利用H2pda与Zn(II)离子反应得到化合物([Zn3(pda)2(SO4)(H2O)4.4H2O])(pda2-=(4-carboxym-ethyl-piperazin-1-yl)-acetic anion)。通过元素分析、FT-IR和X-ray单晶衍射对化合物进行了结构表征。结果表明:标题化合物内含有一个由配体pda2-阴离子和金属Zn(II)离子形成的三维孔洞结构,孔洞空位填充了一个SO42-阴离子。     

[Zn(DMF)6]H2SiW12O40·(CH3)2NH的合成,晶体结构及性质

The title compound [Zn(DMF)₆]H₂SiW₁₂O₄₀·(CH₃)₂NH was synthesized in mixed solvent of aqueous and acetonitrile, and its crystal structure had been determined using single crystal X-ray diffraction. The crystal belongs to monoclinic, space group C2/m, a=2.0654(4)nm, b=1.3306(3)nm, c=1.3194(3)nm, β=119.59(3)°, V=3.1531(11)nm³, D_c=3.606Mg·m^-3, Z=2, R=0.0462, R_w=0.0836. The title compound comprises of a [Zn(DMF)₆]²⁺ unit, a polyanion and a free (CH₃)₂NH molecule. The ESR spectrum of the title compound shows that charge-transfer between organic groups and polyanion takes place under irradiation of the sunlight in solid state. The TG study of the title compound shows that it had four stages of the weight loss, and the increase of the de-composition temperature for the polyanion shows that the stability of the polyanion was enhanced due to the influence of Zn²⁺ ion. CCDC:175866.     

新型三维间排层状钴磷酸盐配合物Co3(PO4)2·6H2O的合成与晶体结构

A new three dimensional layered cobalt phosphate complex Co₃(PO₄)₂·6H₂O, was prepared by hydro-thermal reaction of Co(CH₃COO)₂·4H₂O and H₃PO₄, NH₄VO₃. The crystal structure of the complex was deter-mined by single-crystal X-ray diffraction. The result indicates that it crystallizes in the tetragonal space group I4/m. It rarely occurs in cobalt phosphate complex to form two kinds of coordinate geometry of Co(Ⅱ), six water molecular oxygen atoms surround Co(Ⅰ) and form an octahedron geometry, Co(2) bond to four oxygen atoms from 4PO₄^3- and one water molecular oxygen and build a tetragonal pyramid. The kinetic study shows that the first decomposition stage is governed by A(?)B(?)C mode. CSD: 414600.     

混合价双核锰配合物[(bipy)2Mn(μ-O)2Mn(bipy)2](ClO4)3的合成晶体结构及性能

[Mn₃O(O₂CCH₂Cl)₆(C₅H₅N)₂(H₂O)]·CH₂ClCOO·H₂O在pH=4.5的HOAcNaOAc的缓冲水溶液中和2,2′联吡啶(bipy)反应,制得了混合价双核锰配合物[(bipy)₂Mn(μ-O)₂Mn(bipy)₂](ClO₄)₃·1.5H₂O。该配位化合物的X射线单晶衍射表明,该晶体属单斜晶系,空间群P2₁/c,晶胞参数:a=1.3854(3),b=1.3943(3),c=2.4225(5)nm,β=103.30°,V=4.554(2)nm³,Z=4,D_c=1.448g·cm^-3。其紫外可见光谱在640nm处有一个峰,可指派为桥配体O^2-到Mn(Ⅲ)的电荷迁移光谱.循环伏安实验说明,此配合物在半波电位E_1/2为1.25V处,有一个可逆的氧化还原峰,这相应于(Ⅲ,Ⅳ)态氧化为(Ⅳ,Ⅳ)态,另外在0.37V处有一阴极峰,相应于(Ⅲ,Ⅳ)态还原为(Ⅲ,Ⅲ)态,在0.81V处有一氧化峰,相应于(Ⅲ,Ⅲ)态氧化为(Ⅲ,Ⅳ)态,这两个峰是不可逆的。     

配合物[Cd（1,3-BDC）（L）（H2O）2]·H2O的水热合成、晶体结构和荧光性质

利用水热方法制备了一个新的过渡金属镉配合物[Cd(1,3-BDC)(L)(H2O)2]·H2O(1,3-H2BDC=间苯二甲酸,L=2-(3-吡啶基)-1H-苯并咪唑),并通过元素分析、红外光谱和X-射线单晶衍射方法确定了该配合物的晶体结构.结构分析表明该配合物属于单斜晶系,P21/c空间群,晶胞参数a=1.016 41(6)nm,b=2.088 42(12)nm,c=1.001 38(6)nm,β=106.336 0(10)°,V=2.039 8(2)nm3,Z=4,R1=0.020 7,wR2=0.494.配合物中CdⅡ离子与L配体的1个吡啶N原子、1,3-BDC的4个氧原子和2个配位水的O原子配位,形成七配位的扭曲十面体结构.配体1,3-BDC的桥连相邻的CdⅡ离子形成一维聚合物链,相邻链间通过氢键和π…π作用形成三维超分子网络,并对该配合物的热稳定性和荧光性质进行了研究.     

新型双核Co（Ⅱ）聚合物{[Co2L（MeOH）（H2O）4]n·nH2O}的合成及其晶体结构

采用溶剂热法,丁烷四羧酸(H4L)与水合乙酸钴经配位聚合反应合成了一个新型的双核Co(Ⅱ)聚合物[Co2L(MeOH)(H2O)4]n.nH2O(1),其结构经元素分析和单晶X-射线衍射表征。1属单斜晶系,C2/c空间群,晶胞参数a=2.802 6(3)nm,b=0.816 32(11)nm,c=1.630 1(2)nm,β=119.793(2)°,V=3.236 5(7)nm3,Z=8,Dc=1.925 Mg.cm-3,R1=0.097 5,wR2=0.223 1。1通过H4L桥联形成一维链,通过O-H┈O氢键作用形成了无限延伸的二维网络结构;在1中存在的分子内及分子间氢键使1具有三维网络结构。     

桥联双核配合物[(DPC)2Co2(H2O)5]·2H2O的合成与晶体结构

The new complex formulated [(DPC)₂Co₂(H₂O)₅]·2H₂O (HDPC^- is pyridine-2,6-dicarboxylate) has been synthesized and the crystal structure was determined by X-ray diffraction. The crystal structure of the complex belongs to monoclinic system with space group P2₁/c, a=0.83850(10) nm, b=2.7386(4) nm, c=0.9610(2) nm, β=98.280 (10) °, V=2.1838(6) nm³, Z=4, D_c=1.746 g·cm^-3, μ=1.597 mm^-1. In the crystal the two Co²⁺ are in distorted octahedrons. The part of [Co(DPC)₂] possess an approximate D_2d symmetry, while the part of [OCo₍₂₎(OH₂)₅] has an approximate C₂ symmetry.     

一个双核镍配合物[Ni2(Htda)2(H2O)6]·4H2O的合成、晶体结构和性质

双核金属配合物对于生物化学和磁化学都是非常重要的。在本文中,1,2,3-三氮唑-4,5-二羧酸(H₃tda)配体和硝酸镍在常温常压下反应得到了1个三氮唑桥联的双核镍配合物[Ni₂(Htda)₂(H₂O)₆]·4H₂O (1),并通过元素分析、红外光谱、X-射线单晶衍射、热重分析以及超导量子干涉仪(SQUID)对其晶体结构和磁、热性质进行了表征。晶体数据表明该配合物属三斜晶系,空间群为P1。在配合物1中,2个1,2,3-三氮唑-4,5-二羧酸配体利用2个相邻的氮原子桥联2个金属镍离子形成一个双桥的双核镍配合物。这些双核镍单元又通过体系中存在的大量的氢键相互作用形成了三维超分子骨架。磁性分析显示双核镍单元内镍镍之间存在反铁磁相互作用。     

新型双核配位聚合物Ni2（A`B`T`C`）（phen）2（H2O）4·4H2O的合成及其晶体结构

以A`B`T`C`(2,2’,3,3’-偶氮苯四甲酸)和Phen(邻啡啰啉)为配体,采用溶剂挥发法合成了一种新型双核配位聚合物Ni2(A`B`T`C`)(phen)2(H2O)4.4H2O(1),其结构经X-射线单晶衍射和元素分析表征。1属三斜晶系,空间群P-1,晶胞参数a=9.432(11),b=10.697(12),c=10.751(12),α=87.946(17)°,β=67.756(15)°,γ=76.085(16)°,V=972.6843,Z=12,Dc=4.740 mg.cm-3,μ=4.039 mm-1,F(000)=1 364,R1=0.042 5,ωR2=0.132 9。1中Ni(Ⅱ)与A`B`T`C中的两个羧基氧原子,两个H2O中的两个氧原子和phen中的两个氮原子配位,形成一个畸变的八面体几何构型。Ni(Ⅱ)经配体A`B`T`C桥联形成一维链,链与链之间又通过氢键堆积成三维超分子结构。     

一维链状铜配位聚合物[Cu(m-BDOA)(bipy)·H2O]n的合成与晶体结构

A novel coordination polymer, [Cu(m-BDOA)(bipy)·H₂O]_n (m-BDOA^2-=benzene-1,3-dioxyacetate), was synthesized and characterized by elemental analysis, IR spectra, X-ray single crystal structure analysis. Crystallographic data are as follows: orthorhombic, space group Pna2₁, a=1.606 9(3) nm, b=1.685 9(3) nm, c=0.699 7(1) nm, V=1.8955(7) nm³, Z=4, D_c=1.619 g·cm^-3, μ=1.200 mm^-1, F(000)=948，R=0.038 1, wR=0.038 6. The copper atom is five-coordinated involving two oxygen atoms of different m-BDOA^2- ligand, two nitrogen atoms of 2,2′-bipy ligand and one coordinated water, there is a distorted square pyramidal environment. Two copper atoms are bridged by m-BDOA^2- ligand, forming a one-dimensional chain along a axis. The adjacent distance of Cu…Cu atoms is 0.877 3nm. The crystal network was formed by the intermolecular hydrogen bond and π-packing interactions.     

三维稀土配位聚合物[Ce2(H2btc)(btc)(H2O)2]n的水热合成与晶体结构

含有稀土元素的无机一有机配位聚合物因在光、电、磁及催化等方面具有潜在的应用价值而引起人们的关注．芳香多羧基有机配体在合成配位聚合物和多维超分子研究领域中扮演着重要角色．1，2，4，5-均苯四甲酸(H4btc)由于具有独特的配位能力(btc^4-最多可作为八齿配体)和空间特性，     

新型单核Zn（Ⅱ）配合物{Zn（H2O）6·（pbsa）2·2H2O}的合成、晶体结构及其光学性质

在水中采用回流法合成了Zn(Ⅱ)单核配合物{Zn(H2O)6·(pbsa)2·2H2O(1),pbsa=2-苯基苯并咪唑-5-磺酸阴离子},其结构和性能经UV-Vis,FL,X-射线单晶衍射和TG表征。1属单斜晶系,空间群C2/m,晶胞参数a=23.223(2),b=6.905 6(5),c=11.670 1(9),β=119.660(2)°,V=1 626.3(2)3,Z=2,Dc=1.544 mg·cm-3。1的中心离子为Zn(Ⅱ),与六个水分子配位;pbsa没有与中心离子配位,只起电荷平衡作用;未配位的水分子像节点一样通过氢键将1连接成三维网状的空间结构。1的λmax位于318 nm;在430 nm波长激发下,1的最大荧光发射峰位于425 nm和465 nm。     

一维链状配位聚合物[Cu3(TFSSB)2·(H2O)4·4H2O]n的合成和晶体结构

The title complex [Cu₃(TFSSB)₂·(H₂O)₄·4H₂O]_n (TFSSB=taurine 3-formylsalicylic schiff base) was synthesized by TFSSB and copper(Ⅱ) acetate monohydrate in ethanol solution and the crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic system, space group P2₁ / n，with cell parameters: a=0.927 9(6) nm, b=1.173 0(2) nm, c=1.471(2) nm, β=106.96(2)°, and V=1.531(2) nm³, Z=2, D_c=1.890 g·cm^-3, μ=2.291 mm^-1, F(000)=882, R₁=0.025 9, wR₂=0.065 9. The Cu1 is five-coordinate, the Cu2 is four-coordinate. CCDC: 253298.     

无机-有机杂化硫属化合物[Mn（1，2-dap）2（H2O）]2（μ-Sn2Q6）（Q=S、Se）和[Mn（tren）]2（μ-Sn2S6）的合成、晶体结构与性能

采用溶剂热方法合成了3个多元硫属化合物[Mn（1,2-dap）₂（H₂O）]₂（μ-Sn₂Q₆）（Q=S（1）和Se（2））和[Mn（tren）]₂（μ-Sn₂S₆）（3）,用X-射线单晶衍射测定了化合物的结构,并通过红外光谱、紫外-可见漫反射光谱对其进行了表征。单晶结构解析表明,化合物1和2都属于正交晶系,Pccn空间群（No.56）,晶体结构是由[Mn（1,2-dap）₂（H₂O）]²⁺配合物阳离子和[Sn₂Q₆]^4-二聚体通过Mn-Q键连接而成的[Mn（1,2-dap）₂（H₂O）]₂（μ-Sn₂Q₆）低聚体,相邻的低聚体之间通过氢键相连形成三维结构。化合物3属于三斜晶系,晶体结构是由[Mn（tren）]₂（μ-Sn₂S₆）单元通过氢键连接而成的二维结构。紫外-可见漫反射光谱结果显示化合物1,2和3的带隙分别为2.5,2.1,2.4eV,属于半导体材料。     

一维链状铜配位聚合物[Cu(bpb)0.5(CH3COO)2]n的合成与晶体结构

A coordination complex of [Cu(bpb)_0.5(CH₃COO)₂]_n (bpb=1,4-bis(pyridine-3-aminomethyl)benzene) has been synthesized and characterized by elemental analysis, IR spectra, TG and X-ray single crystal diffraction. The title complex crystallizes in triclinic with space group P1, a=0.771 98(15) nm, b=0.827 62(17) nm, c=1.116 0(2) nm, α=96.71(3)°, β=90.03(3)°, γ=105.39(3)°, and V=0.682 4(3) nm³, Z=2, R=0.042 4, wR=0.091 1. The title complex is composed of dicopper tetracarboxylate units. Copper(Ⅱ) atom asumes a square-pyramidal coordination geometry formed with one pyridyl N atom from bpb and four O atoms from four bridging acetate anions. Two adjacent dicopper tetracarboxylate units are linked into a 1D chain by the bpb ligands, which were further connected by inter-chain hydrogen bonds to form a 2D network structure. CCDC: 667605.     

[U(CO3)3(H2O)2]·2H2O配合物的合成及晶体结构

A uranylcontaining compound [U(CO₃)₃(H₂O)₂]·2H₂O has been synthesized under hydrothermal condition and characterized by X-ray single-crystal analysis. Crystal structural analysis indicates that this compound consists of three CO₃^2- molecules, one U⁶⁺. The results reveal that the title compound presents a 3D frame work built up by O-H…O week hydrogen bonds interactions. The central uranium atom is eight-coordinated through three CO₃^2- molecules and two H₂O. The compound shows a coplanar hexagonal network structure, each hexagon containing a hexagonal hole with a water moleculet. CCDC: 737313.     

配合物Fe(pda)2(H2O)4和[FeCo(pda)4(H2O)4]n的合成与晶体结构

采用水热法合成了2个3-(3-吡啶基)丙烯酸的配合物:Fe(pda)2(H2O)4(1)和[FeCo(pda)4(H2O)4]n(2)(pda=3-(3-吡啶基)丙烯酸),用红外光谱、元素分析、热重-差热以及X-射线衍射单晶结构分析进行了表征.2个配合物都属于单斜晶系,配合物1的空间群为P21/n,配合物2的为P21/c.配合物1是一个pda配体中仅吡啶基氮原子参与配位、而羧基上的氧原子未参与配位的单核结构,通过大量的氢键作用形成三维超分子体系.2是pda配体桥联Fe和Co的异核二维层状配位聚合物;配体吡啶基上的氮原子和羧基上的氧原子都参与了配位,其中羧基采用单齿配位模式.     

铈配合物[Ce（4-aba）3（4-abaH）（phen）2]·H2O的合成与晶体结构

采用普通溶液法合成了单核铈配合物[Ce(4-aba)3(4-abaH)(phen)2]·H2O(4-abaH=对氨基苯甲酸,phen=1,10-邻菲罗啉)。X射线单晶衍射结果表明:该配合物晶体属单斜晶系,P21/c空间群,晶胞参数:a=1.8896(4)nm,b=1.9755(4)nm,c=1.3200(3)nm,β=97.235(2)°,V=4.8880(18)nm3,Mr=1064.06,Dc=1.446 g·cm-3,Z=4,μ=0.996 mm-1。中心铈离子的配位环境为变形的三帽三棱柱体。配合物存在着π-π堆积及丰富的氢键,将配合物扩展为三维超分子结构。