含β-酮亚胺的席夫碱化合物的合成及配位化学研究

【作者】 张奇龙；

【导师】 朱必学；

【作者基本信息】 贵州大学 ， 物理化学， 2008， 硕士

【摘要】 席夫碱化合物在生物化学、配位化学、超分子化学、催化、电化学等方面表现出许多新颖的性能，一直受到化学工作者的普遍重视。近年来，席夫碱配体由单齿发展到多齿和大坏，过渡金属的席夫碱配合物具有独特的结构、性能和广泛的应用研究前景，如氧化还原、催化、荧光材料以及生物体系的化学模拟等。以自组装战略为基础的有机-无机配位聚合物化学是目前国际化学界最跃、前沿的研究领域之一，亦是合成新型有机-无机复合功能材料的最有效的途径之一。为此，我们设计合成了一系列含β酮亚胺的新型Schiff Base化合物；研究它们与金属离子的自组装化学：合成了33个新型的有机-无机配位聚合物和超分子，并通过红外、核磁、元素分析、X-射线单晶衍射等技术表征了它们的结构。本论文的研究工作如下：一、用二胺和乙酰丙酮进行缩合，再与2,5-二巯基-1，3,4-噻二唑进行成环作用，得到了两个新型的含杂原子的席夫碱大环化合物，并用合成大环的中间体Schiff-base配体L和Ni²⁺，Cu²⁺离子反应，得到4个单核的Schiff-base配合物单晶结构。通过核磁共振谱（¹H NMR）、元素分析、质谱、红外光谱、X-单晶衍射等对合成得到的席夫碱配体及其配合物进行了表征。二、合成了一系列以乙酰丙酮、苯甲酰丙酮为端基的柔性Schiff-base配体，并以之同金属离子Co²⁺，Ni²⁺，Cu²⁺，Zn²⁺，Ag⁺进行配位反应得到了17个单核和聚合型的配合物。通过核磁共振谱（¹H NMR）、元素分析、红外光谱、X-单晶衍射等对合成得到的席夫碱配体及其配合物进行了表征。三、合成了一系列以乙酰丙酮、苯甲酰丙酮为端基的手性环己二胺桥联的Schiff-base配体，并以之与金属离子Mn²⁺，Co²⁺，Zn²⁺，Ag⁺，Cd²⁺，La³⁺进行配位反应得到了12个多核型、大环型、聚合型配合物。通过核磁共振谱（¹H NMR）、元素分析、红外光谱、X-单晶衍射等对合成得到的席夫碱配体及其配合物进行了表征。更多还原

【Abstract】 Because of the large flexibility and good coordination capability of schiff base ligands, the studies on Schiff base metal complexes are paid much attention, with lots of novel properties showing in biochemistry, coordination chemistry, supermolecular chemistry, catalysis, electrochemistry, etc. Schiff base ligands are developing from simple, monodentate ligands to multidentate and macrocyclic Schiff base ligands. Transition mental Schiff base complexes possess special structures, properties and widely uses, such as oxidation-reduction, catalysis and chemical simulation for biological systems. The chemistry of organic-inorganic coordination polymers has recently become area of increasing interest. Self-assembly of organic ligands and inorganic metal ions is one of the most efficient and widely used approaches for the construction of organic-inorganic composite materials. In this thesis, a series of new Schiff base ligands by the acetylacetone and benzoylacetone were synthesized. The coordination chemistry based on these new ligands and metal ions was investigated. Totally 33 new coordination compounds were prepared and fully characterized by IR, elemental analysis, X-ray single-crystal diffraction. This main content is shown as follows:Ⅰ. Two Novel Schiff Base macrocyclic compounds have been synthesizedfromethylenediamine, 1,2-propanediamine, acetylacetone and 2,5-dimercapto-1,3, 4-thiadiazole by condensation, brominating and cyclic action. Then. Four complexes were prepared by coordination of the intermediates Schiff base ligands with copper acetate and nickelous acetate, A series of the new Sc hiff base ligands and complexes were characterized by ¹HNMR, elemental analsis, Mass spectroscope, FT-IR and single crystal X-ray diffraction.Ⅱ. The flexible Schiff-base ligands have been synthesized from the acetylacetone, benzoylacetone and diamine. Their coordination chemistry with Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ , Ag⁺ salts was investigated. A series of the new Schiff base ligands and complexes were characterized by ¹HNMR, elemental analsis, FT-IR and single crystal X-ray diffraction.Ⅲ. The Schiff-base ligands have been synthesized from the acetylacetone, benzoylacetone and 1,2-Diaminocyclo hexane. Their coordination chemistry with Mn²⁺, Co²⁺, Zn²⁺, Ag⁺, Cd²⁺, La³⁺ salts was investigated. A series of the new Schiff base ligands and complexes were characterized by ¹HNMR, elemental analsis, FT-IR and single crystal X-ray diffraction.更多还原