配位聚合物[Co2(C13H10NO2)4(4，4′-bipy)2]n的合成、晶体结构、热稳定性及荧光性质

以N-苯基邻氨基苯甲酸(NPA)、CoSO₄和4,4′-联吡啶为原料,溶液法合成了一个新的配位聚合物[Co₂(C₁₃H₁₀NO₂)₄(4,4′-bipy)₂]_n,并对其进行了红外、元素分析、热重、荧光及X射线衍射等表征与研究。测定结果表明,该配合物晶体属三斜晶系,空间群P1,晶胞参数：a=1.086 99(13) nm,b=1.136 23(13) nm,c=1.414 72(16) nm,α=71.886 0(10)°,β=76.374(2)°,γ=66.177 0(10)°,V=1.507 0(3) nm³,D_c=1.409 g·cm^-3,Z=2,F(000)=662。最终GOF=1.028,最终偏离因子R₁=0.043 7,wR₂=0.079 4。中心Co(Ⅱ)离子分别与2个联吡啶N原子,4个羧基氧原子配位形成六配位的变形八面体结构。其中1个NPA分子的羧基以螯合方式与Co(Ⅱ)金属原子配位,另2个NPA分子的羧基以桥联的方式与相邻的2个Co(Ⅱ)离子配位,形成一个双核Co簇的二级构筑单元。此双核Co簇通过4,4′-联吡啶分子连接起来,最终形成形成一维双链梯状结构。     

一维梯状配合物{[Cu2(4,4''-bpy)3(p-Ab)2(H2O)2]·(NO3)2·4H2O}n的晶体结构

合成了一维分子梯状配合物{[Cu2(4,4'-bpy)3(p-Ab)2(H2O)2]·(NO3) 2·4H2O}n(4,4'-bpy=4,4'-联吡啶,p-Ab-=对氨基苯甲酸根离子),该配合物晶体属单斜晶系,P2(1)/c空间群,晶胞参数:a=1.110 7(5) nm,b=1.550 4(3) nm,c=1.450 9(3) nm,β=104.81(3)°,V=2.415 5(12) nm3,Z=2.铜离子周围有3个氧原子和3个氮原子与之配位,其中2个氧原子由对氨基苯甲酸的螯合氧原子提供,另一个氧原子由配位水提供,3个氮原子分别由三个4,4'-联吡啶提供.这六个原子在铜离子周围形成一个畸变的八面体配位环境.配体对氨基苯甲酸只有一种配位形式--双齿螯合,第二配体4,4'-联吡啶的两个氮原子均参与配位,将配合物组装成一维分子梯结构.     

钴配合物[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4的合成与晶体结构研究

用硫酸钴、4,4'-联吡啶和2-磺酸基乙基膦酸合成了一个新颖的钴化合物:[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4,并对其进行了红外.元素分析、热重测试,通过单晶衍射仪测定了其晶体结构.结果表明,配合物属单斜晶系C2/c空间群,分子式为C_(22)H_(45)Co_2N_4O_(22)PS_2,分子量为930.57,晶胞参数为a=19.8456(18),b=11.2957(10),c=34.719(3)(A),β=106.095(3)°,晶胞体积为7477.9(12)(A)~3,Z=8,Dc=1.653 g/cm~3,F(000)=3856,μ=1.131 mm~(-1),最终残差因子R_1=0.0726,wR_2= 0.1719(相对于5612个I>2σ(I)的可观测衍射点).在这个化合物中,二齿配体4,4'-联吡啶把Co(II)桥连成[Co(4,4'-bipy)]~(2+)链.化合物中的[Co(4,4'-bipy)]~(2+)链有三个不同的朝向.2-磺酸基乙基膦酸没有参与配位而是做为一个有机模板剂填充在[Co(4,4'-bipy)]~(2+)链形成的空隙中.     

一维链状钴配位聚合物Co(α-Furoic acid)2 (4,4''- bipy)2 (H2O)2的结构及电化学性质

在甲醇和水的混合溶剂中用呋喃甲酸、4,4'-联吡啶和碳酸钴合成了一种新型配位聚合物[Co(α-Furoic acid)2(4,4'-bipy)2 (H2O)2]. 该配合物晶体属三斜晶系,空间群P 1,晶胞参数:a=1.138 4(4),b=1.138 4(4),c=1.302 9(9) nm;γ=120.0°,V=1.462 3(12) nm3,Dc=1.612 g/cm3,Z=3,F(000)=729. 最终偏离因子R1=0.049 0,wR2=0.143 6. 晶体中钴原子与2个bipy的2个N原子及2个呋喃甲酸根的2个氧原子配位及2个水分子的2个氧原子配位,形成六配位的变形八面体结构,结合晶体结构进行了电化学性质研究. 结果表明,电极反应中电子转移是准可逆的,配合物稳定性好.     

双核钴(Ⅱ)配合物[Co_2(2,2'-bpy)_2(μ-L)_2(L)_2(μ-H_2O)](HL=4-fluorobenzoic acid)的水热合成、晶体结构和磁性研究

通过水热法合成了4-氟苯甲酸桥联的新型双核钴(Ⅱ)配合物[Co2(2,2-bpy)2(μ-L)2(L)2(μ-H2O)](HL=4-fluorobenzoic acid)(1)并测定了其晶体结构。结果表明配合物1属单斜晶系,空间群C2/c,晶胞参数为a=22.204(4),b=15.777(3),c=15.184(3),β=123.71(3)°,Z=4,Mr=1004.65,V=4424.7(15)3,μ=0.829 mm-1,Dc=1.508g/cm3,F(000)=2048,R1=0.0386,wR2=0.1006。配合物1具有双核蝴蝶状结构,中心钴(Ⅱ)离子处于CoN2O4八面体配位环境中,每个钴(Ⅱ)分别与来自一个2,2-联吡啶的2个N原子、三个4-氟苯甲酸根的3个O原子和一个配位水分子的1个O原子配位,两个钴(Ⅱ)被2个4-氟苯甲酸根和1个桥联水分子桥联为双核蝴蝶状结构。分子间通过氢键和π-π堆积作用,构成了3D超分子网状结构。变温磁化率测试结果表明该化合物在5~300K范围内显示反铁磁性。     

光致发光配合物[Au_2(PPh_3)_2(μ-4,4'-bpy)](ClO_4)_2和[Cu_2(PPh_3)_4(CH_3CN)_2(μ-4,4'-bpy)](BF_4)_2的合成和晶体结构

合成了两个在空气中稳定的Au（I）和Cu（I）配合物,并运用元素分析、红外 光谱、荧光光谱和X射线单晶衍射结构表征,[Au_2(PPh_3)_2(μ-4,4'-bpy)] (ClO_4)_2（1）（4,4'-bpy为4,4'-联吡啶）,单斜晶系,空间群P2_1 c,晶胞参 数a = 1.2255(4) nm,b = 0.9973(3) nm,c = 1.8506(6) nm,β = 101.732(5) °,V = 2.2145(11) nm~3,Z = 4,最终偏离因子R = 0.0430,wR = 0.0937。 [Cu_2(PPh_3)_4(CH_3CN)_2(μ-4,4'-bpy)](BF_4)_2（2）,单斜晶系,空间群 P2_1 c,晶胞参数a = 1.3463(3) nm,b = 1.4681(3) nm,c = 2.0608(4) nm,β = 100.387(4)°,V = 4.0066(13) nm~3,Z = 2,最终偏离因子R = 0.0450,wR = 0.1163。两个双核配合物都是利用4,4'-联吡啶桥联配体,形成直线结构,直线 的两端以PPh_3或CH_3CN为端基。Au（I）为2配位,Cu（I）为4配位。两个配合物 均具有光致发光特性,其中配合物1发光来自MLCT激发态,而配合物2则是受配位金 属影响的配体内部发光。     

一维链状钴配位聚合物Co(α-Furoic acid)_2(4,4′-bipy)_2(H_2O)_2的结构及电化学性质

在甲醇和水的混合溶剂中用呋喃甲酸、4,4′-联吡啶和碳酸钴合成了一种新型配位聚合物[Co(α-Furoic ac id)2(4,4-′b ipy)2(H2O)2]。该配合物晶体属三斜晶系,空间群P 1,晶胞参数:a=1.138 4(4),b=1.138 4(4),c=1.302 9(9)nm;γ=120.0°,V=1.462 3(12)nm3,Dc=1.612 g/cm3,Z=3,F(000)=729。最终偏离因子R1=0.049 0,wR2=0.143 6。晶体中钴原子与2个b ipy的2个N原子及2个呋喃甲酸根的2个氧原子配位及2个水分子的2个氧原子配位,形成六配位的变形八面体结构,结合晶体结构进行了电化学性质研究。结果表明,电极反应中电子转移是准可逆的,配合物稳定性好。     

基于2-(4-甲基苯甲酰基)苯甲酸及2,2′-联吡啶的双核铜(Ⅱ)配合物的晶体结构、荧光和磁性(英文)

以2-(4-甲基苯甲酰基)苯甲酸(HL)及2,2′-联吡啶(2,2′-bipy)为配体合成了一个双核铜(Ⅱ)配合物[Cu2(L)4(2,2′-bipy)2]·H2O(1),并对其进行了晶体结构测定。测定结果表明,该配合物晶体属于三斜晶系,空间群为P1,晶胞参数:a=1.012 57(15)nm,b=1.312 5(2)nm,c=1.317 0(2)nm,α=82.985(2)°,β=76.437(2)°,γ=88.290(2)°,V=1.688 7(4)nm3,Dc=1.391 g·cm-3,Z=2,F(000)=732,GooF=1.027,最终偏离因子R1=0.037 5,wR2=0.091 4。在配合物分子中相邻的2个铜(Ⅱ)离子通过2个2-(4-甲基苯甲酰基)苯甲酸根桥联配位连接起来,其端位各与1个2-(4-甲基苯甲酰基)苯甲酸根和1个2,2′-联吡啶分子配位,整个分子形成了双核结构。测定了标题配合物的荧光和磁性,结果表明:当激发波长为608 nm时,配合物在472和476 nm处有2个较强的荧光发射峰;在2~100 K,配合物具有顺磁性。     

三核铜(Ⅰ/Ⅱ)配合物[Cu(en)_2]·[Cu(pht)_2]_2的合成、晶体结构及与DNA相互作用的研究

报道了多核铜配合物[Cu(en)_2]·[Cu(pht)_2]_2(Hpht:苯妥英,即5,5-二苯基-2,2-咪唑烷酮;en:乙二胺)的溶剂热合成、晶体结构及其与DNA的相互作用.该晶体属三斜晶系,P_1~-空间群,晶胞参数:a=0.8453(2)nm,b=1.1878(3)nm,c=1.5674(4)nm,a=101.197(3)°,β=97.690(3)°,γ=103.283(3)°,V=1.476(6)nm~3,D_c=1.480 g/cm~3,Z=1,F(000)=679,μ=1.139nm~(-1),R_1=0.0402,wR_2=0.0962[I>2σ(Ⅰ)],GOF=1.035.XPS和X射线单晶衍射数据显示该配合物分子由混价铜组成,包括两个一价铜和一个二价铜,其中每个Cu(Ⅰ)分别与两个苯妥英配体提供的氮原子配位,N-Cu(Ⅰ)-N的夹角为177°,一个Cu(Ⅱ)与六个配位原子配位(CuN_4O_2),形成一个稍变形八面体结构.配合物与DNA相互作用研究表明,该配合物主要是以插入方式与小牛胸腺DNA结合.     

新型一维链状配位聚合物{[Cu2(dhbd)(bipy)2]·10H2O}n的研究

采用水热法合成了标题配位聚合物{[Cu2(dhbd)(bipy)2]·10H2O}n(H4dhbd=2,3-二羟基丁二酸,bipy=2,2'-联吡啶),通过元素分析、红外光谱、热分析、X射线单晶衍射等技术对其进行了表征.配合物属单斜晶系,空间群C2/c,a=2.1965(4)nm,b=1.0671(2)nm,c=1.3662(3)nm,β=93.50(3)°,Z=4,R=0.0388.晶体的基本构建基元包含10个结晶H2O分子和由两个Cu(Ⅱ)原子、一个采用双二齿螯合配位的2,3-二羟基丁二酸根、两个2,2'-联吡啶形成具有C2旋转轴的U形双核单元,相邻的两个方向相反的U形双核单元通过双羧基O桥联形成沿c轴延伸的一维链;链间籍C-H…O和O-H…O氢键扩展为三维结构.配合物中呈现了一种2,3-二羟基丁二酸与过渡金属配位的新方式.     

Synthesis,Crystal Structure and Thermal Stability of a One-dimensional Chain Cobalt Coordination Polymer [Co(4,4'-bipy)(2,4,6-TMBA)_2(CH_3CH_2OH)_2]_n

A one-dimensional chain cobalt(Ⅱ) coordination polymer with 2,4,6-trimethylbenzoic acid, 4,4'-bipyridine and cobalt perchlorate anhydrous has been synthesized and characterized in the mixture solvent of water and alcohol. Crystal data for this complex: monoclinic, space group C2/c, a = 2.3805(8), b = 1.1464(4), c = 1.5807(5) nm, γ = 128.435(4)°, V= 3.3791(18) nm3,Dc = 1.246 g/cm3, Z = 4, F(000) = 1340, final GooF = 1.009, R = 0.0504 and wR = 0.1287.Structural analysis shows that the cobalt ion is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule and four oxygen atoms from two 2,4,6-trimethylbenzoic acid molecules and two alcohol molecules, giving a distorted octahedral coordination geometry. The result of TG analysis indicates that the title complex is stable till 200 ℃.     

Synthesis,Crystal Structure and Thermal Stability Properties of a Binuclear Copper(Ⅱ) Coordination Polymer {[Cu_2(4,4'-bipy)_2(o-ABA)_4(H_2O)_2][(H_2O)_2]}_n

One-dimensional chain copper(Ⅱ) coordination polymer has been synthesized and characterized in the solvent mixture of water and alcohol with o-acetamidobenzoic acid,4,4'-bipyridine and copper perchlorate.It is of tetragonal,space group P41212 with a=1.57756(10),b= 1.57756(10),c=2.1438(3)nm,V=5.3352(8) nm3,Dc=1.524 g/cm3,Z=4,F(000)=2536,R= 0.0479 and wR=0.0979.The crystal structure shows two coordination modes.The copper(1) is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule and two oxygen atoms from two o-acetamidobenzoic acid molecules,forming a distorted tetrahedral coordination geometry;the copper(2) is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule,four oxygen atoms from two o-acetamidobenzoic acid molecules and two water molecules,generating a distorted octahedral coordination geometry.The result of TG analysis shows that the title complex is stable below 180.0 ℃.     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4''-bipy)(H2O)5]n

A one-dimensional chain coordination polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4'-bipy)(H2O)5]n has been synthesized with cinnamylic acid, 4,4'-bipy and cobaltous chloride as raw materials. Crystal data for this complex: monoclinic, space group P21/c, a - 1.1481(3), b =1.1230(2), c = 1.1759(3) nm, β = 97.054(4)°, V = 1.5046(6) nm3, Mr= 617.50, Dc = 1.363 g/cm3, Z= 2, μ(MoKα) = 0.627 mm-1, F(000) = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt(Ⅱ) ions are linked together by one 4,4'-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt(Ⅱ) ion is coordinated with two nitrogen atoms from two 4,4'-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

Synthesis,Crystal Structure and Electrochemical Properties of a One-dimensional Chain Coordination Polymer [Mn （NAA ）2（ 4,4′-bipy ） （H2O）4]n

A novel one-dimensional chain coordination polymer [Mn（NAAh（4,4′-bipy）（H2O）4], has been synthesized with a-naphthaleneacetic acid, 4,4′-bipy and manganese（Ⅱ） sulfate as raw materials. Crystal data for this complex： monoclinic, space group P21/c, a = 1.1421（2）, b = 1.6337（3）, c = 0.94177（19） nm, β = 112.15（3）°, V = 1.6275（6） nm^3, De = 1.407 g/cm^3, Z = 2, μ（MoKa） = 0.467 mm^-1, F（000） = 722, S = 1.007, R= 0.0412 and wR = 0.1022. The crystal structure shows that two neighboring manganese（Ⅱ） ions are linked together by one 4,4′-bipy molecule, and the whole complex molecule forms a one-dimensional chain structure. Each manganese（Ⅱ） ion is coordinated with two oxygen atoms of two a-naphthaleneacetic acid molecules, two nitrogen atoms of two 4,4′-bipy molecules and two oxygen atoms from two water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were also analyzed.     

一维链状铽配位聚合物{[Tb(p-MBA)2(H2O)2]2·(4，4′-bipy)2}n的合成、晶体结构及荧光分析

A novel one-dimensional chain coordination polymer of terbium(Ⅲ) with p-methylbenzoic acid, 2,2′-bi-pyridine and 4,4′-bipyridine has been synthesized and characterized. The crystal data of this complex C₃₉H₃₇N₃O₈Tb are as follows: monoclinic system, space group P2₁/n, a=0.974 01(10) nm, b=2.605 8(3) nm, c=1.457 77(14) nm, β=96.108(2)°, V=3.678 9(6) nm³, D_c=1.507 g·cm^-3, M_r=834.64, Z=4, μ(Mo Kα)=1.978 mm^-1, F(000)=1 684, R₁=0.032 4, wR₂=0.063 4. The crystal structure of the complex shows that the terbium(Ⅲ) ion is coordinated with eight oxygen atoms, six from five p-methylbenzoic acid molecules and two from two water molecules, respectively, forming the distorted tetraprism geometry. The luminescent property of the complex is also studied. CCDC: 619216.     

Synthesis and Crystal Structure ofa Bipy Bridged Binuclear Cu^Ⅱ Complex Containing Aminomethanesulfonic Acid [Cu2（Sams）2（Bipy）（H2O）2]·（H2O）

The title complex [Cu2（Sams）2（H2O）2（bipy）]·（H2O） 1 （H2Sams = N-（2-hydroxybenzy） aminomethanesulfonic acid, bipy = 4,4′-bipyridine） has been synthesized by the reaction of Cu- （CH3COO）2·H2O, nESams and 4,4′-bipyridine in aqueous methanol. It was characterized by IR, elemental analysis, thermogravimetric analysis （TGA） and X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group P21/n with a= 10.9533（17）, b = 8.3408（13）, c = 16.714（3） A^°, β = 101.295（4）°, V = 1494.3（4） A^°3 and Z = 2. The asymmetric unit is comprised of a tridentate Schiff base Sams^2- anionic ligand, a 4,4′-bipyddine and two coordinated water molecules, thus forming a binuclear copper（Ⅱ） complex. The coordination environment at Cu^Ⅱ center is described as a slightly distorted square pyramidal geometry. Via intermolecular hydrogen bonds C（10）-H（10）…O（3） and C（13）- H（13）…O（3）, an infinite supramolecular chain is yielded. A number of intermolecular hydrogen bonds greatly contribute to the stabilization of the solid-state structure for 1.     

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.     

邻-(4-甲基苯甲酰基)-苯甲酸双核镉(Ⅱ)配合物的水热合成、晶体结构及热稳定性

<正>羧酸因其具有多样的配位方式、羧基氧原子易参与形成氢键以及本身能减缓抗衡离子效应的负电性而被广泛应用于配合物的合成中[1-4]。目前,研究主要集中于苯甲酸及其衍生物构筑的配合物,而其     

一维链状3-碘苯甲酸铽配合物的合成、晶体结构和性质表征

溶液法合成了配合物{[Tb(3-IBA)₃(H₂O)₂]·0.5(4,4′-bipy)}_n(3-IBA=3-碘苯甲酸根;4,4′-bipy=4,4′-联吡啶),并通过X-射线衍射单晶结构分析、红外光谱、紫外光谱、荧光光谱以及热重分析对配合物进行了结构和性质表征。配合物晶体属三斜晶系,P1空间群。该配合物具有一维链状结构。Tb³⁺离子与8个O原子配位,其中6个O原子来自5个3-碘苯甲酸根,2个O原子来自水分子。相邻Tb³⁺离子通过2个双齿桥联的3-碘苯甲酸根联结成一维链状结构。未配位的4,4′-联吡啶分子与配位水分子之间形成氢键,并将相邻的一维链联结起来形成二维网状结构。沿a轴的分子堆积形成一维孔道,是由于相邻一维链的苯环之间部分重叠而形成的。在紫外光照射下,配合物发出很强的绿色荧光。配合物的荧光光谱中,4个峰位于490、544、583和619 nm,分别对应于Tb³⁺离子的⁵D₄→⁷F₆、⁵D₄→⁷F₅、⁵D₄→⁷F₄和⁵D₄→⁷F₃跃迁。     

[Cu(PTA)(Phen)2](p-MBA)(H6O)配合物的合成、晶体结构及电化学分析

The crystal structure of the title complex with the stoichiometric formula [Cu(PTA)(Phen)₂](p-MBA)(H₆O) (Phen=1,10-phenanthroline, PTA=terephthalic acid, p-MBA=p-toluic acid) has been determined by single-crystal X-ray diffraction. The crystal (C₄₈H₄₀CuN₄O₁₀, M_r=896.38) belongs to the monoclinic space group C2/c, with the following crystallographic parameters: a=1.778 6(3) nm, b=1.912 5(3) nm, c=1.389 9(2) nm, β=114.686(2)°, V=4.295 7(12) nm³, D_c=1.386 g·cm^-3, Z=4, μ(Mo Kα)=0.574 mm^-1, F(000)=1 860, final GooF=1.019, R=0.054 0, wR=0.148 3 for 2 644 observed reflections (I>2σ(I)). The crystal structure shows that the copper(Ⅱ) ion is coordinated with two oxygen atoms from one terephthalic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 298809.