【作者】 李文杰；

【导师】 朱东升；

【作者基本信息】 东北师范大学 ， 有机化学， 2010， 硕士

【摘要】 自从1849年以来,有机锡化学开始被研究,在近30年得到了相当好地发展,合成了大量具有特性的有机锡化合物。有机锡羧酸酯被广泛用作催化剂、热稳定剂、杀菌剂、防污涂料及木材防腐剂,各类有机锡羧酸酯的结构模式和生物活性特别是抗癌活性己经成为当今研究的热点。本文以二丁基氧化锡、三苯基氢氧化锡以及三环己基氢氧化锡为底物,以1,4-萘二酸、5-氨基间苯二甲酸、酰亚胺酸等刚性芳香羧酸为配体,合成了八个未见文献报道的有机锡羧酸酯。通过元素分析、红外光谱和核磁共振谱等测试手段对配体及相应的金属配合物进行了表征,并用X-射线单晶衍射测得了配合物的晶体结构。初步研究了配合物1的荧光性能和抗癌活性。本文由以下内容组成:1.利用1,4-萘二酸（H₂L¹）与正丁基氧化锡、三苯基氢氧化锡、三环己基氢氧化锡分别作用,合成了三种金属有机配合物,（n-Bu₂SnL¹）₄·2C₆H₆ （1）、（Ph₃Sn）₂L¹（ONC₃H₇）₂ （2）、（Cy₃Sn）₂L¹ （3）。有趣的是,配合物（1）是一个中心对称,4核36元大环二有机锡二羧酸酯化合物,大环是由二丁基锡和配体交替连接而成。发光性能的研究表明,与配体相比较,配合物（1）荧光强度明显加强。生物活性测试表明,配合物（1）具有良好的抗癌活性。2.利用5-氨基间苯二甲酸（H₂L²）与三苯基氢氧化锡在无水甲苯中加热回流反应,合成了（Ph₃Sn）₂L²（OC₂H₅）₂ （4）,进而形成了含有4核28元的大环（Ⅰ）和48元的大环（Ⅱ）两类大环的有机锡二维层状聚合物。配合物（4）中的锡原子为五配位,构成以锡原子为中心扭曲的三角双锥构型。配合物（4）通过三类不同的分子间的O-H···O氢键的相互作用形成含两类大环的二维的超分子结构。3.首先利用1,8-萘二甲酸酐、苯酐和对氨基苯甲酸、5-氨基间苯二甲酸合成4种酰亚胺酸（HL³, H₂L⁴, HL⁵, H₂L⁶）;紧接着利用它们分别与三苯基氢氧化锡反应,合成了四种金属有机配合物,Ph₃SnL³ （5）、（Ph₃Sn）₂L⁴·C₇H₈ （6）、Ph₃SnL⁵ （7）、（Ph₃Sn）₂L⁶ （8）。这些配合物中都存在分子间氢键的相互作用,从而在配合物（5）、（7）、（8）中形成一维链状结构,同时在配合物（6）中,利用这些相互作用形成二维的超分子结构。更多还原

【Abstract】 The chemistry of organotin has been studied since 1849 and developed considerably during last 30 years, highlighting the syntheses of a number of complexes with interesting properties. Organotin complexes have been used extensively as catalysts, stabilizers, biocides, anti-fouling agents and wood preservatives. In recent years, the investigations on the structure mode and biological activities, especially anti-tumor activity of organotin complexes have become the focus on organotin chemistry.In this paper, eight organotin carboxylates were synthesized by the reactions of di-n-butyltin oxide, triphenyltin hydroxide, trihexamethylenetin hydroxide with rigid aromatic carboxylic acid ligands including naphthalene-1,4-dicarboxylic acid, 5-amino-isophthalic acid, imide acid. The ligands and their metal complexes were characterized by elemental analysis, FT-IR and 1H NMR spectroscopy, and the structures of the complexes were determined by single crystal X-ray diffraction analysis. The luminescent property and antitumour activities of complexe 1 were preliminary studied. The dissertation contains the following works:1. Three complexes （n-Bu₂SnL¹）₄·2C₆H₆ （1）、（Ph₃Sn）₂L¹（ONC₃H₇）₂ （2）、（Cy₃Sn）₂L¹ （3） have been synthesized by the reaction of naphthalene-1,4-dicarboxylic acid （H₂L¹）and di-n-butyltin oxide, triphenyltin hydroxide, trihexamethylenetin hydroxide. Interestingly, complex （1） has a centrosymmetric tetranuclear diorganotin dicarboxylate with 36-membered macrocycle, which is formed by n-Bu2Sn and ligand alternately linking. Luminescent property study of complex （1） has shown that the fluorescent intensity strengthened markedly compared with ligand. Pilot studies indicated that complex （1） has shown good antitumour activities.2. The complex （Ph₃Sn）₂L²（OC₂H₅）₂ （4） has been synthesized by the refluxing reaction of 5-amino-isophthalic acid （H₂L²）and triphenyltin hydroxide in anhydrous toluene, then forms two-dimensional layered polymer containing tetranuclear 28-membered （Ⅰ） and tetranuclear 48-membered （Ⅱ） two types of macrocycles. In the molecular structure of complex （4）, Sn atoms are five-coordinated and present the distorted trigonal bipyramidal geometry structures. Through three different types of intermolecular O-H···O hydrogen bonding interactions, complex （4） forms 2D structures containing two types of macrocycles.3. First, four kinds of imide acids （H2L3、HL4、H2L5、HL6） have been prepared by using 1,8-naphthalene dicarboxylic anhydride, phthalic anhydride with p-aminobenzoic acid, 5-amino-isophthalic acid, then four complexes Ph₃SnL³ （5）、（Ph₃Sn）₂L⁴·C₇H₈ （6）、Ph₃SnL⁵ （7）、（Ph₃Sn）₂L⁶ （8） have been synthesized by the reaction of corresponding imide acids and triphenyltin hydroxide. There exist intermolecular O-H···O hydrogen-bonding interactions in these complexes. Through hydrogen bonding interactions, one-dimensional chains are formed in complex （5）, complex （7） and complex （8）; 2D structure is formed in complex （6）.更多还原