【作者】 李静；

【导师】 邢永恒；

【作者基本信息】 辽宁师范大学 ， 无机化学， 2009， 硕士

【摘要】 近年来,以羧酸为主要构筑单元,利用共价键和分子间的相互作用组装超分子配合物的研究方法受到广泛关注,它们不仅结构富有特色,而且在催化、电磁材料、微孔材料、非线性光学材料等方面有潜在的应用前景。超氧化物歧化酶（SOD）是一种金属酶,它广泛的存在于好氧生物体内并且起到非常重要的作用。因此有关含有水杨醛类席夫碱SOD模拟化合物的研究迅速发展起来。本文以多羧酸类配体和三（2–氨基乙基）胺缩水杨醛席夫碱为配体在常温条件下合成得到一系列过渡金属配合物,对它们的结构、性质进行了初步研究。主要工作集中在以下几个方面:1.以柔性多羧酸（丁二酸和戊二酸）为第一配体,3,5–二甲基吡唑为辅助配体,在溶液中合成得到4个过渡金属配合物:[Zn（Hdmpz）₂（O₂C（CH₂）₂CO₂）]_n （1）, Ni₃（Hdmpz）₄（HOOC（CH₂）₂CO₂）₂（O₂C（CH₂）₂CO₂）₂（CH₃OH）₂ （2）, HB（C₅H₇N₂）₃Ni（C₄H₅O₄）（C₅H₈N₂）₂·2H₂O （3）,Co₃（Hdmpz）₂（HOOC（CH₂）₃CO₂）₂（O₂C（CH₂）₃CO₂）₂（CH₃OH）₄ （4）。红外光谱和单晶衍射表明,配合物1是由丁二酸配体桥连起来的锌配位聚合物,中心金属锌位于变形的八面体的中心,配体丁二酸的两端的羧基采取双齿螯合的配位方式与金属锌配位。配合物2和4是由羧酸配体（丁二酸和戊二酸）桥连起来的中心对称的三核过渡金属配合物,其中丁二酸和戊二酸的羧基都是采取μ₃–η²–η²和μ₂–η¹–η¹与金属配位,它们与金属的配位方式相似。而配合物3是含有聚吡唑硼酸盐镍的羧酸化合物,其中金属镍与丁二酸单齿配位。同时,配合物1–4晶体结构中含有丰富的氢键及弱相互作用,将配合物组装成多维的超分子结构。2.以刚性多羧酸（2,6–吡啶二羧酸）为第一配体,3,5–二甲基吡唑为辅助配体,在溶液中合成得到2个过渡金属配合物: [Co（2,6–PDC）（Hdmpz）₃]·H₂O （5）, [Zn（2,6–PDC）（Hdmpz）₂] （6）。红外光谱和单晶衍射表明,配合物5和6是由2,6–吡啶二羧酸和3,5–二甲基吡唑为有机配体,与过渡金属形成的六配位的单核结构,同时在分子中也存在氢键和弱相互作用。3.在室温条件下采用液液合成方法得到两个三（2–氨基乙基）胺缩水杨醛席夫碱(C₆H₁₂N₄)（C₇H₆O）₃ （7）及过渡金属配合物（C₆H₇N₄） Mn （C₇H₅O）₃·H₂O （8）,通过红外光谱和单晶结构测定得知:配合物8是三（2–氨基乙基）胺缩水杨醛席夫碱过渡金属锰的配合物,其中金属锰位于六配位的扭曲的八面体几何中心。更多还原

【Abstract】 In recent years, supramolecular complexes constructed by carboxylic acids through both covalent bond and weak interactions have attracted great interest of chemists. This is because of their intriguing structural frameworks but also account for their potential applications in catalysis, electronic and magnetic materials, microporous materials and nonlinear optics materials. SOD is a kind of metalloenzyme, which exists widely in the body of aerobionts and plays an important role. The investigation of SOD mimics complexes with Schiff bases （in particular derived from the salicylaldehyde） are developed rapidly. In this thesis, a series of complexes based on multicarboxylic acids and Tri（2-aminoethyl）amine have been successfully synthesized in solution conditions, their structure and properties were investigated.1. Four metal complexes were synthesized in the solution with the main liganaliphtiacids （succinate/ glutarate） and the auxiliary ligand Hdmpz: [Zn（Hdmpz）₂（O₂C（CH₂）₂CO₂）]_n （1）, Ni₃（Hdmpz）₄（HOOC（CH₂）₂CO₂）₂（O₂C（CH₂）₂CO₂）₂（CH₃OH）₂ （2）, HB（C₅H₇N₂）₃Ni（C₄H₅O₄）（C₅H₈N₂）₂·2H₂O （3）,Co₃（Hdmpz）₂（HOOC（CH₂）₃CO₂）₂（O₂C（CH₂）₃CO₂）₂（CH₃OH）₄ （4）. IR spectra and single crystal X-ray diffraction analysis show that complex 1 is a polymer that is interconnected by bridging succinate moieties in chelating bidentate coordination modes with Zinc. Complexes 2 and 3 are tri-nuclear structures; both of them have two types of bridging–coordinated modes of carboxylate ligands （μ₃–η²–η² ,μ₂–η¹–η¹）. Moreover, 3 is nickel succinate complex containing poly（pyrazolyl）borate, thereinto, complex 3 is coordinated by bridging succinate moiety in chelating monodentate coordination modes with nickel.And there are rich intra- or intermolecular hydrogen bonds and weak interactions in the crystals of 1–4, thereby forming a set of supramolecular frameworks.2. Two metal complexes were synthesized in the solution with the main rigid ligand Acids（Pyridine-2,6-dicarboxylic acid） and the auxiliary ligand Hdmpz: [Co（2,6–PDC）（Hdmpz）₃]·H₂O （5）, [Zn（2,6–PDC）（Hdmpz）₂] （6）. IR spectra and single crystal X-ray diffraction analysis show that complex 5 and 6 are in a six-coordinated mode, which features anomalistic octahedral geometry. In addition, there are hydrogen bonds and weak interactions in the crystals of 5, 6.3. Two complexes were synthesized in the solution with Salicylidene tri（2-aminoethyl）amine （7） and Salicylidene tri（2-aminoethyl）amine manganese （8） complexes. X-ray diffraction analysis show that complex 8 is in a six coordinated mode with anomalistic octahedral geometry.更多还原