配位聚合物{[Co(4,4′-bpy)(H2O)4](Fum)·4H2O}n的合成和晶体结构

The complex {[Co(4,4′-bpy)(H₂O)₄](Fum)·4H₂O}_n(where 4,4′-bpy = 4,4′-bipyridine and Fum = fumarate) was synthesized and characterized by X-ray diffraction. The complex consists of one-dimensional chains containing cobalt(Ⅱ) ions bridged by 4,4′-bpy molecules. The six-coordination of Co²⁺ is achieved by means of four water molecules. The fumarate is not coordinated to cobalt ion while it forms hydrogen bonds with coordinated and non-coordinated water molecules and extends the structure into three-dimensional hydrogen bonding network. CCDC: 190488.     

氢键构筑的新颖微孔配位聚合物[Co2(Hisor)2·(4,4′-bpy)2(H2O)2]·4,4′-bpy的合成与结构

A novel microporous coordination polymer [Co2(Hisor)2(4,4′-bpy)2(H2O)2]·4,4′-bpy was synthesized by hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analysis and IR spectrum. The crystal belongs to the monoclinic system and space group is P2/n with a=1.040 6(3) nm, b=1.138 8(4) nm, c=1.854 7(6) nm, β=102.991(6)°, V= 2.141 6(12) nm3, Z=2, Dc=1.443 Mg/m3, Mr=930.62, μ=0.842 mm-1, F(000)=952, GOF= 1.072, R=0.065 4, wR=0.146 8[I>2σ(I)]. There are two crystallographically independent Co(Ⅱ) ions in the title complex. The Hisor2- and 4,4′-bpy link the metal ions into 2D grids with dimension of 0.522 3 nm×1.138 8 nm. There are O—H…O and N—H…O hydrogen bonds in the complex resulting in the formation of 3D network with 1D channels, in which are free 4,4′-bpy molecules.     

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。     

一维链状锌配位聚合物[Zn(4，4′-bipy)·(o-ABA)2·(H2O)2]n的合成、晶体结构及热稳定性

锌是重要的生命元素,在生物体内锌以多种形式参与代谢过程,包括糖类、脂类、蛋白质与核酸的合成与降解,对生命体系有着特殊的生物活性和催化作用[1].模拟合成以锌、铜等为中心离子的配位聚合物并对其结构进行研究,将为人们认识生命体系中与这些金属离子相关的生命现象提供重要的信息[2,3].4,4′-联吡啶是一种线状双基刚性配体,无支链,空间位阻少,有较好的桥联作用,它与金属离子在自组装过程中能形成各种一维,二维,及三维空间结构的配位聚合物[4～7].     

一维链状配位聚合物[M(H2bpb)(H2O)4](SO4)2·6H2O[M=Zn(Ⅱ)，Cu(Ⅱ)]的合成及晶体结构表征

设计并合成了一个含吡啶基团的柔性配体：N，N′-Bis(3-pyridylmethyl)-1，4-benzenedimethylamine(bpb)。通过bpb与硫酸锌及硫酸铜反应得到了两个新型具有一维链状结构的配位聚合物：[M(H₂bpb)(H₂O)₄](SO₄)₂·6H₂O[M=Zn(Ⅱ) 1，Cu(Ⅱ) 2]。X-射线晶体结构测定表明，这两个     

一维配位聚合物{[Co(dpa)(H2O)4]·(dpdo)·(H2O)}n(H2dpa=2,2’-联苯二酸,dpdo=N,N’-二氧化-4,4’-联吡啶)的晶体结构和光谱性质

采用水热合成法制备了一个一维配位聚合物{[Co(dpa)(H2O)4].(dpdo).(H2O)}n(1)(H2dpa=2,2′-联苯二酸,dpdo=N,N′-二氧化-4,4′-联吡啶),通过红外光谱、紫外光谱、元素分析、XRPD、TGA和X-射线单晶衍射进行了表征。Co(Ⅱ)原子采取了畸变的八面体构型,6个配位氧原子分别来自于2个dpa2-配体和4个配位水分子。每一个dpa2-配体桥联2个Co髤中心,每一个Co(Ⅱ)原子与2个dpa2-配体配位进而形成了21螺旋链结构。借助溶剂水分子的连接作用,螺旋链之间通过多种O-H…O氢键作用形成了2D网格,通过dpdo和2D网格之间多种类型的氢键作用形成了三维超分子结构。测定了室温下聚合物1的固体荧光光谱。     

二维层状配位聚合物{[Cd(p-CMSP)(Him)(H2O)]·3H2O}n

The novel coordination polymer {[Cd(p-CMSP)(Him)(H₂O)]·3H₂O}_n ( p-CMSP^2-=p-(carboxymethoxy)phenylthioacetate, Him=imidazole) was synthesized by the reaction of Cd(NO3)₂, imidazole and p-(carboxymethoxy)phenylthioacetic acid in an aqueous solution, and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The crystal structure is of monoclinic, space group P2₁/c with a=1.144 0(2) nm, b=1.876 7(4) nm, c=0.877 89(18) nm, β=106.31(3)° and V=1.808 9(7) nm³, Z=4, R=0.023 2, wR=0.051 4. Each Cd(II) atom displays a distorted octahedral coordination geometry, defined by three carboxyl O atoms from different p-CMSP^2- ligands, one S atom from thioether, one N atom from imidazole and one water molecule. Adjacent Cd(II) ions are bridged by p-CMSP^2- groups, resulting in a 2D layer structure. The adjacent Cd…Cd distances are 0.492 7 nm and 1.144 0 nm. Furthermore, such layers are linked through hydrogen bonds to form supramolecular network. CCDC: 269474.     

多孔配位聚合物{[Cd2（tpom）（tpa）2]·（DMF）（H2O）3}n的合成及表征

由四(4-吡啶氧甲基)甲烷(tpom)和对苯二甲酸(tpa)与Cd(NO3)2.4H2O合成了配位聚合物{[Cd2(tpom)(tpa)2].(DMF)(H2O)3}n,通过元素分析、红外光谱、X-射线粉末衍射、热重、X-射线单晶衍射对配位聚合物的结构进行了表征。结果表明,标题化合物属于单斜晶系C2/c空间群,晶胞参数为a=3.4747(17)nm,b=2.0899(10)nm,c=1.4292(10)nm,β=111.642(5)°,V=9.647(9)nm3,Z=8,Dc=1.374 g.cm-3,F(000)=3984.0,μ=0.939 mm-1,其6586个可观测点的结构偏差因子R1=0.0566,wR2=0.1408。结构分析表明,对苯二甲酸连接镉离子形成含双核镉(CdCOO)2的平面,四(4-吡啶氧甲基)甲烷连接双核镉形成具有两重穿插pcu拓扑构型的三维骨架。     

异金属1D配位聚合物{[CuLZn·CuLZn(H2O)]·H2O}n的合成、表征、性质及晶体结构

合成了铜锌异金属一维链状配位聚合物, 并通过IR谱、元素分析、热分析的方法对其进行了表征和性质研究, 利用X射线单晶衍射方法对晶体结构进行了测定. 该化合物为具有{[CuLZn·CuLZn(H₂O)]·H₂O}_n化学组成的一维链状配位聚合物(H₄L=N-(3-羧基水杨醛)-N′-(2-羟基苯甲酰基)乙撑二胺), 其结构单元为由两个不对称四核单元组成的两种不同的四核环, 这两种环由羧基桥联形成了1D链状配位聚合物.     

一维配位聚合物{[Co(dpa)(H2O)4] ·(dpdo)·(H2O)}n(H2dpa=2, 2′-联苯二酸, dpdo=N, N′-二氧化-4, 4′-联吡啶)的晶体结构和光谱性质

采用水热合成法制备了一个一维配位聚合物{[Co(dpa)(H₂O)₄] ·(dpdo)·(H₂O)}_n (1)(H₂dpa=2, 2′-联苯二酸, dpdo=N, N′-二氧化-4, 4′-联吡啶), 通过红外光谱、紫外光谱、元素分析、XRPD、TGA和X-射线单晶衍射进行了表征。Co(Ⅱ)原子采取了畸变的八面体构型, 6个配位氧原子分别来自于2个dpa^2-配体和4个配位水分子。每一个dpa^2-配体桥联2个Co(Ⅱ)中心, 每一个Co(Ⅱ)原子与2个dpa^2-配体配位进而形成了2₁螺旋链结构。借助溶剂水分子的连接作用, 螺旋链之间通过多种O-H…O氢键作用形成了2D网格, 通过dpdo和2D网格之间多种类型的氢键作用形成了三维超分子结构。测定了室温下聚合物1的固体荧光光谱。     

配位聚合物[Mn(4，4′-bpy)1.5(H2O)3](ClO4)·(4，4′-bpy)(L)·H2O的水热合成和晶体结构

The title compound, [Mn(4,4′-bpy)_1.5(H₂O)₃](ClO₄)·(4,4′-bpy)(L)·H₂O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°, γ=91.118(2)°, V=1.884 0(4) nm³, Z=2, M_r=780.10, D_c=1.375 g·cm^-3, μ=0.483 mm^-1, F(000)=812, R=0.055 4, wR=0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4′-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4′-bipyridine molecules. CCDC: 615707.     

二维配位聚合物[K2(5-nbdc)2Cd(Ⅱ)·imH·H2O]∞的合成和晶体结构(英)

The crystal structure of the title complex, [K₂(5-nbdc)₂Cd(Ⅱ)·imH·H₂O]_∞ (5-nbdc=5-nitro-1,3-benzenedicarbonate, imH=imidazole) has been determined by X-ray diffraction analysis. The crystal data are: tetragonal, space group P4₁, M_r=694.93 for CdC₁₉H₁₂N₄O₁₃K₂, a=1.018 6(10) nm, b=1.018 6(10) nm, c=2.436 7(5) nm; Z=4, V=2.528 2(6) nm³, F(000)=1 376, D_c=1.826 Mg·m^-3, μ=1.267 mm^-1. The title polymeric complex exhibits a two-dimensional framework, in which adjacent Cd(Ⅱ) ions are bridged by μ-O₄-5-nitro-1,3-benzenedicarbonate groups forming one-dimensional chains that are further linked by μ-O₃-5-nitro-1,3-benzenedicarbonate groups into two-dimensional anion rectangle sheets with large 32-membered rings. The strong π-π stacks of the benzene rings link these adjacent sheets into a three-dimensional van der Waals network. CCDC: 245527.     

配位聚合物{[Zn(CF3COO)2(C5H5ON)]·H2O}n的合成、晶体结构及表征

new coordination polymer {[Zn(CF₃COO)₂(C₅H₅ON)]·H₂O}_n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C₅H₅ON) in methanol medium for the first time. The structure of the coordination polymer was confirmed by IR, ¹H NMR, elemental analysis and thermal analysis. The crystal structure of the coordination polymer was also determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P2₁/m, and crystallographic data of the coordination polymer are: a= 0.863 1(4) nm, b=0.717 7(3) nm, c=1.116 4(5) nm, α=γ=90°, β=107.542(6)°, V=0.659 4(5) nm³; D_c=2.037 g·cm^-3; Z=2; F(000)=400; μ=1.969 mm^-1. Zinc(Ⅱ) atom lies at the center of an octahedron formed by the coordination of zinc atom and six O atoms which come from four different trifluoroacetate ions and two different 3-hydroxypyridine molecules where each trifluoroacetate ion and 3-hydroxypyridine are coordinated to two different zinc ions to form coordination polymer. CCDC: 253909.     

一维链状钴配位聚合物{[Co(C4H4O5)(H2O)2]·H2O}n的合成与晶体结构

One dimensional chain cobalt coordination polymer has been synthesized with malic acid and cobalt(Ⅱ) chloride anhydrous, and characterized by the element analysis, IR, TGA and single crystal X-ray diffraction structure analysis. The title complex crystallizes in monoclinic system with space group P2₁, a=0.575 61(9) nm, b=0.905 86(14) nm, c=0.841 02(13) nm, β=105.350(2)°; V=0.422 88(11) nm³, Z=2, D_c=1.924 Mg·m^-3, μ=2.044 mm^-1, F(000)=250, and final R₁=0.029 3, wR₂=0.074 2. The crystal structure shows that the cobalt ion is coordinated with four oxygen atoms from two different malate molecules and two oxygen atoms from two water molecules respectively, forming a distorted octahedral coordination geometry. Two adjacent cobalt(Ⅱ) atoms are bridged by one malate groups in bis-monodentate mode, constructing a one dimensional chain structure along b axis, with the adjacent Co…Co distance being 0.530 9 nm. Moreover, the molecules are packed in three-dimensional supramolecular network though the intermolecular hydrogen bonds. CCDC: 704441.     

配位聚合物[Cd2(BDC)2(obix)2]·H2O的合成、晶体结构和荧光性质

用水热合成方法得到1个新的配位聚合物[Cd2(BDC)2(obix)2]·H2O(H2BDC=对苯二甲酸,obix=1,2-(二亚甲基)二咪唑).配合物晶体属三斜晶系,P1空间群.晶体结构表明:镉原子与3个对苯二甲酸上的5个氧原子,2个1,2-(二亚甲基)二咪唑中的2个氮原子配位形成扭曲的五角双锥配位构型.2个Cd(Ⅱ)原子通过两个羧基桥联形成一个双核Cd2单元,再通过配体连接成二维层状结构,层与层之间通过C-H…O氢键和弱的π-π相互作用形成三维超分子结构.室温下配合物具有较强的荧光发射光谱.     

一维链状镉配位聚合物[Cd(phen)(2，4，6-TMBA)2(H2O)]n的水热合成、晶体结构及热稳定性

在甲醇和水的混合溶剂中用2，4，6-三甲基苯甲酸(2，4，6-TMBA)、邻菲咯啉(phen)、高氯酸镉为原料采用水热法合成了一维链状配位聚合物Cd(phen)(2，4，6-DMBA)₂(H₂O)。该配合物晶体属四方晶系，空间群I4₁。晶体中镉原子与1个邻菲咯啉的2个N原子、2个2，4，6-三甲基苯甲酸酸根中的3个羧基氧原子及1个水分子中的氧原子配位，晶胞参数:a=2.042 5(7) nm，c=1.395 2(5) nm，V=5.820(3) nm³，D_c=1.454 g·cm^-3，Z=8，F(000)=2 608，GooF=1.064，R₁=0.034 8，wR₂=0.070 4。形成六配位的变形八面体结构。对晶体进行了热稳定性分析，结果表明:配合物在240.0 ℃以下稳定性好。     

一维链状钴配位聚合物{[Co(4，4′-bipy)(C9H8O3N)2](H2O)4}n的溶剂热合成、晶体结构及热稳定性

One novel coordination polymer {[Co(4,4′-bipy)(C₉H₈O₃N)₂](H₂O)₄}_n with p-acetamidobenzoic acid and 4,4′-bipy has been synthesized. It was characterized as crystallizing in the triclinic space group P1, with: a=1.138 1(2) nm, b=1.165 2(2) nm, c=1.223 3(2) nm, α=88.47(3)°, β=88.00(3)°, γ=65.78(3)°, V=1.478 4(4) nm³, D_c=1.446 g·cm^-3, Z=1, F(000)=670. Final GooF=1.106, R₁=0.041 5, wR₂=0.110 4. The crystal structure shows that the cobalt(Ⅱ) ion is lined with one 4,4′-bipy molecule, forming a one-dimension chain with Z-type structure, which coordinated with two nitrogen atoms of two 4,4′-bipy molecules and four oxygen atoms from two p-acetamidobenzoic acid molecules, giving a distorted octahedral coordination geometry. The result of TG analysis shows that the title complex was stable under 230.0 ℃. CCDC: 741932.     

{(n-Bu4N)2[Mo2O2S6Cu6Br4(4，4′-bipy)3]·0.5H2O}n的合成与晶体结构

Cluster coordination polymer {(n-Bu₄N)₂[Mo₂O₂S₆Cu₆Br₄(4,4′-bipy)₃]·0.5H₂O}_n (4,4′-bipy=4,4′-bipyridine), has been synthesized and characterized by X-ray crystallography. The polymeric anion {[Mo₂O₂S₆Cu₆Br₄(4,4′-bipy)₃]^2-}_n is composed of secondary building units (SBUs) [MoOS₃Cu₃], Br atoms and 4,4′-bipy ligands. Two secondary building units [MoOS₃Cu₃] and a double parallel 4,4′-bipy ligands form an octanuclear rectangular metallamacrocycle with the dimension of 1.13×0.39 nm², which is further connected by single bridging 4,4′-bipy ligands to form a 1D zigzag structure. Crystal data for compound 1: C₆₂H₉₇N₈O_2.50S₆Br₄Cu₆Mo₂, M=2 079.68, Triclinic, P1, a=0.982 40(10) nm, b=1.293 70(10) nm, c=1.737 4(2) nm, α=97.810(10)°, β=101.390(10)°, γ=108.520(10)°, V=2.005 1(4) nm³, Z=2, D_c=1.722 g·cm^-3, F(000)=1 039, μ(Mo Kα)=4.055 mm^-1, the final R=0.040 7, wR₂=0.097 2. CCDC: 236407.     

配位聚合物{[Co2(HBTC)2(H2O)6]·C4H10N2·2H2O}n的水热合成、结构表征及荧光性质

采用水热法合成了配位聚合物[Co2(HBTC)2(H2O)6]·C4H10N2·2H2O}n(H3BTC为1,3,5-均苯三羧酸,C4H10N2为哌嗪),通过X射线单晶衍射、红外光谱和荧光光谱进行表征,并用TGA研究了该配位聚合物的热稳定性.晶体属三斜晶系,P1空间群,a=1.05437(9)nm,b=1.05485(9)nm,c=0.71482(5)nm,α=102.4623(28)°,β=91.3500(42)°,γ=111.0186(29)°,V=0.72018(10)nm3,Mr=764.37,Dc=1.762g·cm-3,Z=1,μ(MoKα)=1.25mm-1,F(000)=394,R=0.0307,wR=0.0815.晶体的基本构建单元中包含2个Co()中心、2个配位的HBTC分子和6个配位的水分子.基本构建单元通过相互链接形成具有“Z”型结构的一维配位聚合链,链间通过两种不同的氢键(O—H…O和N—H…O)相互作用,进而形成具有三维骨架结构的微孔晶体,微孔大小为0.71nm×0.82nm.荧光光谱表明,常温下用λex=312nm的光激发后,配位聚合物在329nm处出现强烈的荧光发射.     

二维层状配位聚合物[Cd(4，4′-bipy)(2，4-Cl2C6H5OCH2COO)2]n的合成、晶体结构及荧光性质

具有多维高度有序框架结构的配位聚合物由-于其在分子识别和催化、光电性质、磁性等方面表现出的独特性能.引起了人们广泛的研究兴趣[1-3].