【作者】 高健；

【导师】 陆路德； 汪信； 杨绪杰；

【作者基本信息】 南京理工大学 ， 应用化学， 2004， 博士

【摘要】 配位化合物在金属酶的模拟，新材料的开发等方面具有重要的研究价值，近年来得到了长足的发展。本文以新型有机多胺配体为基础，合成了系列双核Cd（Ⅱ）穴合物、带羟乙基手臂的双核Cd（Ⅱ）环合物、一种新型三足式的Zn（Ⅱ）配合物及自组装有机多胺Cu（Ⅱ）配合物；采用元素分析、红外光谱、电喷雾质谱等分析手段对产物进行了谱学表征；通过X-射线衍射解析了八种化合物的单晶结构；通过琼脂扩散抑菌法测定了Cd（Ⅱ）配合物的毒性及其它配合物的抑菌性能；研究了两种Cu（Ⅱ）配合物的磁学性质及电化学性质。全文的主要内容如下： 利用氨基乙腈及丙烯腈的亲核加成、氢化反应合成了不等臂有机多胺化合物2-氨基乙基-二（3-氨基丙基）胺，两步反应的收率分别为82％、71％；产物经多种谱学手段表征确证。通过X-射线衍射首次得到了中间产物二（2-氰基乙基）氨基乙腈的晶体结构。 在高氯酸镉存在下，通过2-氨基乙基-二（3-氨基丙基）胺与2，6-二甲酰基-4-R-苯酚的[2+3]席夫碱缩合反应获得了六种穴合物[Cd₂Lⁿ]（当R=CH₃，CH₃O，C（CH₃）₃，F，Cl，Br,n=1，2，3，4，5，6），并通过元素分析、红外光谱、电子光谱、电喷雾质谱等分析手段对产物进行了谱学表征；实验中发现[Cd₂L¹]是不稳定的，在甲醇溶液中缓慢水解，经历了两个月的放置后，其中的一个Schiff碱C=N键的双键打开，并与一个甲醇分子发生加成反应，产生了一个新的双核Cd（Ⅱ）穴合物[Cd₂L^h]。X-射线衍射表明该晶体属三斜晶系，空间群P-1，Cd（1）周围有六个配位原子，构成了扭曲八面体的配位构型，Cd（2）处于七配位环境中，形成了带帽的八面体构型。利用细菌作为指示生物测定了以上七种Cd（Ⅱ）穴合物的毒性。 通过2-[二（2-氨基乙基）氨基]乙醇和2，6-二甲酰基-4-R-苯酚钠的缩合得到了四种带羟乙基手臂的双核Cd（Ⅱ）环合物（当R=CH₃，CH₃O，F，Cl，n=7，8，9，10），通过元素分析、红外光谱、电子光谱、电喷雾质谱等分析手段对产物进行了谱学表征和研究。通过X-射线衍射解析了三种双核Cd（Ⅱ）环合物的结构。[Cd₂L⁹]晶体属单斜晶系，空间群P2₁／c，两个Cd（Ⅱ）原子都处于七配位的带帽八面体构型中。[Cd₂L⁷]和[Cd₂L¹⁰]皆属三斜晶系，空间群P-1，晶体内皆存在着配位异构现象，是一类新型的配位复晶。这两个晶体分子中都包含了两个具有不同配位构型的阳离子，其中一个阳离子单元中两个Cd（Ⅱ）离子的配位环境与[Cd₂L⁹]非常相似；而另一个阳离子单元，一个Cd（Ⅱ）原子处于七配位的带帽八面体构型中，另一个Cd（Ⅱ）原子处于六配位的八面体构型。利用细菌作为指示生物研究了双核Cd（Ⅱ）环合物的毒性。 通过2-氨基乙基-二（3-氨基丙基）胺与吡啶-2-醛的缩合反应制备了一种新型三足式席夫碱单核Zn（Ⅱ）配合物[ZnL]（ClO₄）₂，进行了谱学表征、晶体结构解析和抑菌活性中文摘要博士论文测定。Zn处于三个亚胺氮原子N（2）、N（4）、N（6）及三个毗睫环上的氮原子N（3）、N（5）、N（7）的六配位环境中，形成了扭曲的三角反棱柱（TAp）配位构型。琼脂扩散抑菌实验结果表明该配合物对四种对受试微生物都表现了较强的抑菌性能。 通过分子自组装合成了一种桥联的双核铜配合物，该配合物的结构由元素分析、红外光谱、电喷雾质谱、热重分析和单晶X一射线衍射所确证。两个铜离子由一个4，4’-联毗咤分子桥联，每个Cu（II）离子处于N4O的五配位环境，并形成了两个扭曲的三角双锥配位构型。琼脂扩散抑菌实验结果表明该配合物对五种对受试微生物都表现了一定的抑菌性能。变温ESR及变温磁化率结果表明该配合物内存在着弱的铁磁相互作用。循环伏安测定显示了两个准可逆的氧化还原波。 合成了一种新型的单核Cu（II）配合物，并通过元素分析、红外光谱、电喷雾质谱、热重分析和单晶X一射线衍射确证其结构。Cual)离子处于N4O的五配位环境，并形成扭曲的三角双锥配位构型。该配合物对五种对受试微生物都表现了一定的抑菌性能。变温ESR及变温磁化率结果表明该配合物内存在着弱的反铁磁相互作用。循环伏安测定显示了一个准可逆的氧化还原波。关键词:有机多胺，大环配合物，Schiff碱，自组装，晶体结构，配位异构，抑菌性能更多还原

【Abstract】 Mimic study and new material exploitation of metal complexes have, for many years, been an active area of research, growing interest in which continues to expand. Based on new organic polyamine, a series of bicadmium (II) cryptates [Cd2Ln] (n = 1, 2, 3, 4, 5, 6), bicadmium (II) complexes [Cd2Ln] (n = 7, 8, 9, 10) with hydroxyethyl pendants, a new tripodal complex [ZnL](ClO4)2, and two self-assembly Cu(II) compounds were synthesized and characterized by spectral characterization such as elemental analysis, IR, ES-MS. A total of eight crystal structures of these compounds were determined by X-ray single crystal diffraction. The toxicity of [Cd2Ln] and the antimicrobial activity of other complexes were evaluated though agar diffusion method. Magnetism and electrochemical properties of the two Cu(II) complexes were also studied.A new inequilateral organic polyamine 2-aminoethyl-bi(3-aminopropyl)amine was synthesized by addition and hydrogenation reactions of aminoacetonitrile with acrylonitrile for the first time. The yields of the production in the two-step reactions are 82% and 71%, respectively. The structure of the title compound was confirmed by spectral characterization. The crystal structure of intermediate bi(2-nitrilethyl)aminoacetonitrile has been determined by single-crystal X-ray diffraction.Six bicadmium (II) cryptates [Cd2Ln] were synthesized by [2+3] Schiff base condensation of 2-aminoethyl-bi(3-aminopropyl)amine with sodium2,6-diformyl-4-R-phenolate (when R = CH3, CH3O, C(CH3)3, F, Cl, Br, n = 1, 2, 3, 4, 5, 6, respectively) in the presence of Cd2+. The structures were confirmed by spectral characterization such as elemental analysis, IR, ES-MS, electronic spectrum and electrical conductivity. However, [Cd2L1] were found not stable, its hydrolysis proceeds more slowly in the methanol solution. Two months later just one imine function was hydrolyzed and solvent addition, and no ring opening to yield cryptate [Cd2Lh], which crystallizes in the triclinic system, space group P-I. Cd(l) locates in a N4O2 coordination environment and forms a distorted tetragonal bipyramid, Cd(2) lies in a N4O3 coordination environment and possesses a monocapped-octahedral geometry. The toxicity of complexes was evaluated by testing antimicrobial activity against bacterial strands.Four bicadmium (II) complexes [Cd2Ln] with hydroxyethyl pendants were synthesized by [2+2] Schiff base condensation of 2-[bis(2-aminoethy)amino]ethanol with sodium 2,6-diformyl-4-R-phenolate (when R = CH3, CH3O, F, Cl, n = 7, 8, 9, 10, respectively) in the presence of Cd2+. The structures of them were confirmed by spectral characterization such aselemental analysis, IR, ES-MS, electronic spectrum and electrical conductivity. Crystals of complex [Cd2L9] were monoclinic, space group P21/c. Both Cd (II) atoms were hepta-coordinated with the coordination surrounding of monocapped-octahedral geometry. While [Cd2L7] and [CdaL10] crystals were isolated as triclinic, space group P-1. Coordination isomerism was found in the crystal structure. Coordination number and coordination geometry of Cd ions in one cationic unit of [Cd2L7] and [Cd2L10] are much similar to that of [Cd2L9], while in another cationic unit, one Cd atom is N3O4 hepta-coordinated, and another Cd atom lies in an N3O3 coordination environment and possesses a distorted octahedral geometry. The toxicity of complexes was evaluated by testing antimicrobial activity against bacterial strands.A new tripodal complex [ZnL](ClO4)2 was synthesized by Schiff base condensation of 2-aminoethyl-bi(3-aminopropyl)amine with 2-pyridinecarbaldehyde in the presence of Zn2+ and characterized by X-ray diffraction and spectral analysis. Zn atom rendered six-coordinate in a trigonal "antiprism geometry. The complex was valued for its antimicrobial activity against bacterial strands using the agar diffusion method. It was found to be active against the four test bacterial organisms.A bridged dinuclear Cu(II) complex was synthesized by molecular assembly method, the structure was confirmed by elemental analysis, IR, ES-更多还原