【作者】 李伟强；

【导师】 孟祥茹；

【作者基本信息】 郑州大学 ， 应用化学， 2011， 硕士

【摘要】 苯并咪唑及其衍生物构筑的功能配合物呈现出独特的光学性质、催化性质以及生物活性,同时还具备配合物和复合高分子的特点,近些年来,越来越多的人开始把目光投向这个领域。本文以不对称氮杂环化合物2-(1H-咪唑-1-甲基)-1H-苯并咪唑(imb)为主配,在丁二酸、间苯二甲酸、邻苯二甲酸、均苯三酸及均苯四酸(H2adi、1,3-bdc、1,2-bdc、btc及dpa)这一系列羧酸辅助配体的存在下,采用水热合成的方法,构筑了6个结构新颖的锌配合物[Zn(imb)3]4·(NO3-)·H2O (1), [Zn(adi)2-(imb)·1.5H2O]n (2),{[Zn2(1,3-bdc)2-2(imb)2]·3H2O}n (3), [Zn2(1,2-bdc)2-2(imb)2]n (4), [Zn(btc)2(imb)2] (5),{[Zn4(dpa)2(imb)4]·4H2O}n (6),并通过单晶X-射线衍射确定了它们的晶体结构。配合物1是一个四核结构,配体以两种配位模式直接与中心金属配位；在1的基础上引入丁二酸,得到了一个由二维网通过互相穿插形成的三维结构的配合物2；引入间苯二甲酸或邻苯二甲酸,得到了配合物3和4,两者分别呈现二维层状结构和一维链状结构；引入均苯三甲酸得到单核配合物5；引入均苯四甲酸得到三维网络结构的配合物6。同时,我们用2-(1H-咪唑-1-甲基)-1H-苯并咪唑为前躯体,氧化得到了一个新的具有多个配位点的羧酸配体,并以该配体采用水热合成的方法得到了具有三维结构的配合物7。我们对配体2-(1H-咪唑-1-甲基)-1H-苯并咪唑,引入的羧酸配体以及配合物1-6的固态荧光性能做了初步研究,结果表明尽管六个配合物结构差别很大,但是配合物的荧光强度与配体相比都有明显的减弱甚至没有荧光发射,且羧酸配体的引入对配合物的荧光强度没有明显的影响。另外,我们对配合物1-4和6的热稳定性进行了研究,研究发现：由于配合物1-3和6的结构中游离基团的存在,导致它们的起始分解温度都比较低,稳定性较差,而配合物4的稳定性很好。更多还原

【Abstract】 The functional complexes built by benzimidazole and its derivatives present unique optical properties, catalytic properties or biological activity, and also possess the characteristics of polymer and composite macromolecule, as a result, increasing attention has been paid on this field in recent years. In this paper, we used an unsymmetrical N-heterocyclic compound 2-(1H-imidazole-l-methyl)-1H-benzimidazole(imb), in the existing of the second ligands succinic acid,1,3-Benzenedicarboxylic acid,1,2-Benzenedicarboxylic acid, 1,3,5-Benzenetricarboxylic acid or 1,2,4,5-Benzenetetracarboxylic acid (H2adi, 1,3-bdc,1,2-bdc, btc or dpa) to react with Zn(II) ions through hydrothermal syntheses technology, and obtained a series of zinc complexes:[Zn(imb)3]4·(NO3-)·H2O (1), [Zn(adi)2-(imb)·1.5H2O]n (2),{[Zn2(1,3-bdc)2-2(imb)2]·3H2O}n (3), [Zn2(1,2-bdc)2-2(imb)2]n (4), [Zn(btc)2(imb)2] (5),{[Zn4(dpa)2(imb)4]·4H2O}n (6). Crystal structures have been determined by single crystal X-ray diffraction:complex 1 is a tetranuclear structure, and the ligands coordinate with center Zn(II) ions by two different modes; based on 1, we obtained complex 2 by using of succinic acid,2 indicates three-dimensional structure through the intersecting of the two-dimensional networks; by using of 1,3-BDC and 1,2-BDC, we obtained complex 3 and 4, they display two dimensional layered structure and one-dimensional chain structure, respectively; complex 5 is a mononuclear structure; 6 indicates three-dimensional network structure. Otherwise, we used 2-(1H-imidazole-l-methyl)-1H-benzimidazole as the precursor to synthesize a new carboxylic ligand which possesses abundant coordination sites. We have obtained complex 7 which displays three-dimensional structure based on this carboxylic ligand, using hydrothermal syntheses technology.The investigation of fluorescent properties for the free ligand 2-(1H-imidazole-l-methy1)-1H-benzimidazole, carboxylic ligands and complexes 1-6 have been observed. The results show that the fluorescence intensity of the six complexes are significantly weaker than the ligand, and the existence of carboxylic ligands can not affect their fluorescence emission features. In addition, we also investigated the thermal properties for complexes 1-4 and 6. The results show that complexes 1-3 and 6 begin to decompose at low temperature and are less stable as the existence of radical groups, complex 4 possesses satisfactory thermal stability.更多还原