N-苯基亚氨基二乙酸桥联的双核铜配合物的合成、表征与晶体结构

由Cu(Ⅱ)、2，2′-联吡啶(邻菲咯啉)与N-苯基亚氨基二乙酸在溶液中组装得到2个双核配合物[Cu₂(L)₂(2，2′-bipy)₂]·8H₂O (1)、[Cu₂(L)₂(phen)₂]·2H₂O (2)(H₂L=N-苯基亚氨基二乙酸，2，2′-bipy=2，2′-联吡啶，phen=邻菲咯啉)。用元素分析、红外光谱、热重分析等进行了表征，并测定了其晶体结构。晶体结构表明，配合物1的晶体属三斜晶系，空间群P1;配合物2的晶体属单斜晶系，空间群P2₁/c。在这2个双核配合物中，中心铜离子的配位形式均为五配位的畸变四方锥构型，配体L中的N原子没有参与配位，而是采用1个羧基的1个氧原子与Cu²⁺离子螯合、另1个羧基上的1个氧原子以μ₂-桥联的配位模式连接2个Cu²⁺离子。     

双核铜配合物{Cu[μ-S2P(C2H5O)2](C10H8N2)}2的合成和晶体结构

Binuclear Copper (Ⅰ) Complex {Cu[μ-S₂P(C₂H₅O)₂](C₁₀H₈N₂)}₂ was synthesized and characterized by elemental analysis, IRand X-ray diffraction analysis.The crystal belongs to triclinic system, space group P1 with Z = 1, cell dimentions are a = 1.0613 (5), b = 1.0723 (3), c = 0.9397 (2) um, a = 111.11 (4), β = 115.57(6), γ = 85.28(2)°, V= 0.8583(6) nm³.The structure was refined to R = 0.039 and Rw = 0.042 for 2527 reflection with Ⅰ≥3σ(Ⅰ).The complex exists as a centrosymmetric dimer with a Cu-S-P-S-Cu-S-P-Schair eight-membered ring in which Cu atoms are bridged by di-μ-S-P-Sgroups.     

Cu[C5H3N(CCH3=N-C6H5)2]2(PF6)2配合物的合成、晶体结构和热分解反应动力学

The title complex Cu[C₅H₃N(CCH₃=N-C₆H₅)₂]₂(PF₆)₂ has been synthesized by reaction of Schiff base C₅H₃N(CCH₃=N-C₆H₅)₂ and cupric sulfate in toluene solution. The crystal structure was determined by X-ray diffraction method and the chemical formula weight of the complex is 1041.85. The crystal structure belongs to triclinic system with space group P1 and cell parameters: a=12.6470(10)?, b=14.123(2)?, c=15.613(2)?;α=66.150(10)°,β=79.470(10)°,γ=78.290(10)°, V=2481.6(5)?³, Z=2, D_c=1.394Mg·m^-3 and F(000)=1064. The final R[I >2σ(I)]:R₁=0.0668, wR₂=0.1927; R(all data): R₁=0.1133, wR₂=0.2357. The Cu(Ⅱ) was coordinated by six nitrogen, at the same time the Cu(Ⅱ) formed a distorted octahedron, besides the angles and planes of this compound were discussed . The result of kinetics of the thermal decomposition indicated that the first step of it is 2 series chemical reactions, the function of machanism is f(a)=(1-a)², and the activation energy is 144.64E/kJ. CCDC: 180872.     

N′-乙基-N-哌嗪基二硫代氨基甲酸铜(Ⅱ)配合物Cu(S2CNC4H8NC2H5)2的晶体结构及谱学研究

合成了标题化合物Cu(S₂CNC₄H₈NC₂H₅)₂,得到深棕色柱状晶体。晶体属三斜晶系,空间群为P1。中心Cu(Ⅱ)离子分别与来 自2个N′-乙基-N-哌嗪基二硫代氨基甲酸的4个硫原子配位,形成略微扭曲的平面四方配位构型。4个Cu-S键的键长范围0.220 10(11)～0.220 34(13) nm;Cu-S键的FT-Raman伸缩振动峰在134.921 cm^-1;ESR谱表明Cu(Ⅱ)离子处于对称中心;其局部配位构型属于D_2h群;热分析表明标题化合物在753.15 ℃时分解为金属Cu。     

配合物[Cu(HPHAc)2(py)2](H2PHAc=苯羟乙酸，py=吡啶)的合成和晶体结构

The novel copper(Ⅱ) complex with α-hydroxyphenylacetic acid (H₂PHAc) and pyridine (py) ligands, [Cu(HPHAc)₂(py)₂], has been synthesized and characterized by elemental analysis and IR spectroscopy. Its crystal structure was determined by single crystal X-ray diffraction techniques. The crystal belongs to monoclinic with space group C2/c. The cell parameters are: a=1.712 5(3) nm, b=1.533 2(2) nm, c=0.963 42(14) nm, β=111.866(2)°, V=2.347 6(6) nm³, and D_c=1.483 Mg·m^-3, Z=4, F(000)=1 084. The structure was refined to final R₁=0.071 4, wR₂=0.166 1. The complex has a six-coordinated distorted octahedral geometry, in which copper(Ⅱ) ion coordinates with two carboxylic oxygen atoms and two hydroxyl oxygen atoms from the two α-hydroxyphenylacetic acid ligands, two nitrogen atoms from the two pyridine ligands. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 255346.     

草酰胺桥联异三核配合物Cu(NiL)2(ClO4)2的合成、光谱表征和晶体结构(英)

A novel oxamido-bridged trinuclear complex Cu(NiL)₂(ClO₄)₂(where H₂L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,3-dien) has been synthesized and characterized by elemental analysis, IR spectrum, UV-Visible spectrum and single crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P2₁/n. The lattice parameters are: a=1.052 4(6) nm, b=1.182 1(6) nm, c=1.586 2(9) nm, β=91.657(9)°, and V=1.972 6(19) nm³, Z=2. The results show that the coordination geometry around copper(Ⅱ) in the title complex is hexa-coordinated octahedron. CCDC: 232608.     

多硫二硫烯铜配合物(n-Bu4N)[Cu(cddt)2]和(Ph4P)[Cu(cddt)2]的合成、表征及其结构

Two copper complexes with a new multi-sulfur 1,2-dithiolene ligand, C[Cu(cddt)₂] (C=tetrabutylammoni-um, n-Bu₄N⁺; tetraphenylphosphonium, Ph₄P⁺; cddt = 4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3 dithi-olate) have been synthesized and characterized by electrochemical studies, IR, EA, etc. The structure of (Ph₄P)[Cu(cddt)₂] was determined by single crystal X-ray analysis. The complex was crystallized in the triclinic, space group P1 with the cell dimensions a=10.460(2)?, b=13.000(3)?,c=16.270(3)?, α=86.68(3)°,β= 71.92(3)°,γ=66.66(3)° and Z=2. R₁=0.0548, wR₂=0.1358 for 6786 independent reflections. The four S atoms surround the Cu atom [CuS₄] core is a square-planar environment.     

不对称大环双核铜(Ⅱ)配合物[Cu2(C23H26Cl2N4O2)](ClO4)2的合成、晶体结构及磁性

大环双核铜(Ⅱ)配合物由N,N′-二甲基-N,N′-二(3-甲酰基-5-氯水杨醛)乙二胺和1,3-丙二胺,与铜(Ⅱ)反应形成的,经过X-射线单晶衍射结果表明：a=0.871 05(16) nm,b=0.957 78(18) nm,c=1.810 4(3) nm,β=100.761(18)°,V=1.483 8(5) nm³,Z=2,D_c=1.762 Mg·m^-3,μ=1.85 mm^-1,F(000)=796,and final R₁=0.061,wR₂=0.126。晶体结构表明：两个铜离子位于双核大环中间,与大环的胺、亚胺以及酚羟基的氧进行配位。磁性结果表明配合物为反铁磁性。     

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.     

2-氨基-5-硝基吡啶乙酸根桥联双核铜配合物的合成和晶体结构

2-氨基-5-硝基吡啶与Cu(CH3COO)2反应生成一个新的乙酸根桥联的双核铜配合物[Cu(CH3COO)2(C5H5N3O2)]2.2H2O.该配合物中,铜原子与一个吡啶环上N原子和四个乙酸根上O原子配位形成五配位的四方锥构型.其晶胞参数为:单斜晶系,空间群P21/c,a=0.834 5(8),b=2.001(2),c=0.808 1(8)nm,β=96.734(4)°,V=1.340(2)nm3,Z=2,Mr=657.37,Dc=1.629 g/cm3,F(000)=652,μ=1.663 mm-1,R1=0.060 4,wR2=0.126 4.电子吸收光谱在207 nm处有吸收;电子发射光谱在419 nm处有发射峰.并用IR和元素分析对配合物进行了表征.     

配合物[Cu(H2O)(C12H8N2)2].2ClO4的合成、性质及晶体结构

合成了配合物[Cu(H2O)(C12H8N2)2]*2ClO4(C12H8N2为1,10-邻菲咯啉),用元素分析、摩尔电导、红外光谱及电子光谱进行了表征,并测定了配合物的晶体结构.该晶体属单斜晶系,空间群为CC;晶胞参数a=1.9177(2)nm,b=0.81994(0)nm,c=1.62458(14)nm,β=100.104(6)°;V=2.5419(4)nm3,Z=4,F(000)=1300,DC=1.693g/cm3,R=0.0430,wR=0.1195.中心铜(Ⅱ)离子与两个1,10-邻菲咯啉的四个N原子和一个水分子的氧原子配位,形成了一个变形的三角双锥结构.     

铜配合物[CuL2(ClO4)2]的合成、晶体结构及热稳定性(L=3-对溴苯基-4-对甲苯基-5-(2-吡啶基)-1，2，4-三氮唑)

以3-对溴苯基-4-对甲苯基-5-(2-吡啶基)-1,2,4-三氮唑(L)作为配体,合成了1个铜配合物trans-[CuL2(ClO4)2],对其进行了红外、电喷雾质谱、热重分析和单晶结构表征,该配合物属于三斜晶系,空间群P1,a=0.829 29(15)nm,b=0.854 48(16)nm,c=1.502 7(3)nm,α=83.517(2)°,β=89.200(2)°,γ=73.064(2)°,V=1.011 9(3)nm3,Z=1,R1=0.041 2。单晶结构表明,铜离子处于1个扭曲的八面体配位环境中,2个高氯酸根离子呈反式配位,每个配体L通过三氮唑上的1个氮原子和吡啶氮原子参与配位。热重分析表明该配合物在310℃开始发生分解。     

二吡啶甲基胺配合物修饰的肿瘤靶向性硅核壳纳米球(英文)

运用油包水微乳液方法制备了二吡啶甲基胺(dpa)及其锰(Ⅱ)和铁(Ⅲ)配合物修饰的Gd-DTPA配合物硅核壳纳米球,其中二吡啶甲基胺锰(Ⅱ)和铁(Ⅲ)配合物修饰的纳米球粒径分别为60和5nm。体外MRI成像研究表明3种纳米球能显著提高肿瘤细胞的磁共振成像效果,具备良好的肿瘤靶向性。生物活性数据显示三价铁配合物修饰的纳米球具备成像和抑制细胞生长的双重功能,而锰配合物修饰的纳米球不能抑制肿瘤细胞的生长,可作为低毒性的肿瘤成像剂。实验结果显示肿瘤靶向性配合物修饰的纳米球可发展成为新型多功能肿瘤靶向性纳米药物。     

[Cu(NBOCTB)](ClO4)2·2DMF的合成、晶体结构和热分解过程研究

制备了二(N,N-二甲基甲酰胺)-高氯酸N,N,N'',N''-四[(1''-苄基-2''-苯并咪唑)甲基]-1,2-环己二胺合铜(Ⅱ){[Cu(NBOCTB)](ClO4)2·2DMF}.X射线测定表明其晶体属三斜晶系,空间群P1,晶胞参数α=1.1851(5)nm,b=1.2255(3)nm,c=2.5237(5)nm;α=92.37(2)°,β=98.01(2)°,γ=107.82(3)°,V=3.442(4)nm3,M=1403.93,Z=2,Dx=1.36g/cm3,μ=4.60cm(-1),F(000)=1470.TG-DTG技术研究结果表明,配合物的热分解过程分为以下4个阶段:(19941106-1597-1.jpg)     

苯丙烯酸桥联的双核镉配合物[Cd(cinnamato)2(Phen)]2的水热合成和晶体结构

A cadmium complex [Cd(cinnamato)₂(Phen)]₂ was synthesized by the reaction of cinnamic acid, phenanth-roline (phen), and Cd(ClO₄)₂·6H₂O. It crystallizes in triclinic, space group P1, with a=1.142 1(13) nm, b=1.157 6(13) nm, c=2.106 1(2) nm, α=80.307(2)°, β=77.334(2)°, γ=71.630(2)°, V=2.563 4(5) nm³, D_c=1.521 g·cm^-3, Z=2, M_r=586.90, μ=0.891 mm^-1, F(000)=1 184, the final R=0.031 7, wR=0.067 5. The crystal structure shows that the cadmium ion is coordinated with two nitrogen atoms from one phen molecule and five oxygen atoms respectively from three cinnamic acids, giving a pentagonal bipyramid coordination geometry. CCDC: 687380.     

配合物[Cu(CAM)(H2O)2]的水热合成与结构表征

A copper(II) complex [Cu(CAM)(H₂O)₂], (CAM=4-hydroxypyridine-2,6-dicarboxylic acid), has been hydr-othermally synthesized and characterized by elemental analysis, IR, and X-ray diffraction single crystal structure analysis. It belongs to triclinic system, with space group P1, a=0.783 3(3) nm, b=0.796 5(3) nm, c=0.798 6(3) nm, α=100.340(6)°, β=93.768(6)°, γ=109.348(5)°, V=0.458 3(3) nm³, Z=2. The copper(II) ion is 5-coordinated and exhi bits a distorted square pyramidal coordination environment. The two coordinated aqueous molecules and the oxygen atoms from the ligand generate the intermolecular hydrogen bonds, which result in the 2D supramolecular network. CCDC: 227156.     

新颖双核铜配合物[Cu2(C7H19N3O)2(C10H8N2)](ClO4)4·H2O的合成、晶体结构及表征

生物体内由金属离子构成的水解酶的活性中心结构和催化机理是物物无机化学领域研究的热点问题[1~4].     

N-邻苯二甲酰甘氨酸双核铜(Ⅱ)配合物的合成、晶体结构及与DNA的作用

合成了新的双核铜(Ⅱ)配合物：[Cu₂(DMSO)₂(ODPA)₄]·2DMSO(其中,DMSO=二甲基亚砜,ODPA=N-邻苯二甲酰甘氨酸)。通过X-射线单晶衍射测定了该配合物的结构。配合物晶体属于三斜晶系,空间群P1,晶胞参数：a=1.036 1(2) nm,b=1.127 3(2) nm,c=1.212 6(2) nm,α=84.084(2)°,β=81.765(3)°,γ=82.163(2)°;晶胞体积V=1.383 6(4) nm³,晶胞结构基元数Z=1,D_c=1.508 g·cm^-3,最后的残差因子：R=0.075 0,wR₂=0.192 7。用紫外和荧光光谱等方法研究了配合物与DNA的相互作用。结果表明,配合物以部分插入方式与DNA作用,凝胶电泳实验结果表明,该配合物能够切割pBR322 DNA成Form Ⅱ。     

N-邻苯二甲酰甘氨酸双核铜(Ⅱ)配合物的合成、晶体结构及与DNA的作用

合成了新的双核铜(Ⅱ)配合物:[Cu₂(DMSO)₂(ODPA)₄]·2DMSO(其中,DMSO=二甲基亚砜,ODPA=N-邻苯二甲酰甘氨酸)。通过X-射线单晶衍射测定了该配合物的结构。配合物晶体属于三斜晶系,空间群P1,晶胞参数:a=1.036 1(2) nm,b=1.127 3(2) nm,c=1.212 6(2) nm,α=84.084(2)°,β=81.765(3)°,γ=82.163(2)°晶胞体积;V=1.383 6(4) nm³,晶胞结构基元数;Z=1,D_c=1.508 g·cm^-1,最后的残差因子:R=0.075 0,wR₂=0.192 7。用紫外和荧光光谱等方法研究了配合物与DNA的相互作用。结果表明,配合物以部分插入方式与DNA作用,凝胶电泳实验结果表明,该配合物能够切割pBR322 DNA。     

蝎型铜配合物：Cu2[ μ-pz]2[HB(pz)3]2和Cu[B(pz)4]2的合成、结构及热分解动力学性质

本文设计合成了两种以聚吡唑硼酸盐、吡唑为配体的铜配合物Cu₂[ μ-pz]₂[HB(pz)₃]₂(1)和Cu[B(pz)₄]₂(2)(pz：吡唑(C₃H₄N₂))。运用元素分析、红外光谱对配合物进行了表征，并用X-ray衍射测定了它们的晶体结构。非等温热分解动力学研究表明：配合物1的热分解反应分两步，配合物2的热分解反应一步进行。通过计算，配合物1热分解的第一步反应的可能机理为成核与生长，n=1/4；第二步反应的可能机理为化学反应。其非等温动力学方程分别为：dα/dT=A/β e^-E/RT·1/4(1-α)[-ln(1-α)]^-3和dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能分别是520.37 kJ·mol^-1和149.65 kJ·mol^-1；指前因子lnA分别是118.06 s^-1和28.10 s^-1。配合物2热分解的可能机理为化学反应。其非等温动力学方程为：dα/dT=A/β e^-E/RT·(1-α)²。分解反应的表观活化能是111.41 kJ·mol^-1；指前因子lnA是21.20 s^-1。