【作者】 田秀梅；

【导师】 王吉德；

【作者基本信息】 新疆大学 ， 无机化学， 2008， 硕士

【摘要】 席夫碱(Schiff base)类化合物由于其在催化、模拟生物酶及抗体、分子识别等方面的应用,长期以来一直是一个研究的热点。其中,最早和最多被研究的是水杨醛类席夫碱,水杨醛类Schiff碱是一类由水杨醛与胺缩合而得到的含有N、O配位原子的配体,易于制备并且具有良好的生理活性作用,与各种金属离子具有很高的配位活性和丰富多样的配位方式,多年来一直是研究的重点。水杨醛Schiff碱及其配合物应用于分子催化和生物模型方面,同时其所具有的发光性、光致变色性、吸波性、顺磁及反磁性等性质在新材料开发与应用方面都具有潜在的重要意义。本文在前期实验的基础上,选取两种双苯甲醛缩二乙烯三胺Schiff碱配体并进行还原,得到两种新的含氮化合物;同时得到了五种水杨醛席夫碱类金属配合物的单晶,并对其荧光性质进行了研究。本文共分为五部分:(1)评述了席夫碱类配合物的研究现状、应用及发展趋势,同时介绍了席夫碱类化合物的还原工作。(2)本文采用硼氢化钠作为还原剂,将两种双席夫碱配体:N1-(4-羟基-3-甲氧基苯次甲基)-N2-(2-(4-羟基-3-甲氧基苯次甲氨基)乙基)-1,2-乙二胺(席夫碱1)和N1-(4-羟基苯次甲基)-N2-(2-(4-羟基苯次甲氨基)乙基)-1,2-乙二胺(席夫碱2)还原得到两种新的含氮类化合物:N1-(4-羟基-3-甲氧基苄基)-N2-(2-(4-羟基-3-甲氧基苄氨基)乙基)-1,2-乙二铵盐(L1·3HCl)和N1-(4-羟基苄基)-N2-(2-(4-羟基苄氨基)乙基)-1,2-乙二铵盐(L2·3HCl),通过元素分析,红外(IR),核磁氢谱(1H NMR),质谱(MS)及紫外吸收光谱表征确定了两种化合物的结构。采用pH电位法测定了配体的质子化常数及其金属配合物的稳定常数,将所得数据带入Repro40和Repro程序得到配合物各种型体随pH的分布曲线。(3)本文合成了水杨醛缩三乙四胺双席夫碱镍、铜的金属配合物,通过元素分析,X-射线单晶衍射分析,确定了配合物的准确结构,并对配合物的性质进行了初步的推断。(4)水杨醛与三乙烯四胺按3:1比例反应得到一种双席夫碱-咪唑啉配体,液相合成了此配体的过渡金属(Ni、Cu、Zn)双核配合物,通过元素分析、红外(IR)、核磁氢谱(1H NMR)、X-射线单晶衍射分析等手段确定了配合物的结构,同时在室温下测定了三种配合物的荧光性质,结果表明:铜和镍的配合物没有荧光性质,而锌配合物荧光性较强,因而增大了其做为荧光材料的应用可能性。通过理论计算,对配体及其锌配合物的荧光性质进行进一步的探讨,解释了荧光强度发生变化的原因。(5)简要总结了本文的工作内容,对席夫碱类过渡金属配合物的前景及今后的工作进行了展望。更多还原

【Abstract】 Schiff bases compounds have attracted a lot of attentions for a long time, because of their application in catalysis, simulating enzyme, antibody, and molecular identification and so on. Of these, the earliest and most research was on the Salicylideneamine. Salicylideneamine stands for a sort of N, O-donating ligands deriving from condensation of salicylaldehyde and amines, which with easy preparation, good physical stability and with very high activity and various coordination manners with metal ions, over the years it has been the focus of the study. Salicylideneamine and their complex were used in catalytic and biological models, and their properties of luminousness, photoluminescence, absorbing, magnetism and anti- magnetism will make them have the potential significance in the developments and applications of new materials.On the basis of early experiments, two bis-Schiff bases were selected and reducted by NaBH4, and two new nitrogenous compounds were obtained. In addition, five crystals of complexes with the salicylideneamine have been obtained, and the fluorescent properties have also been studied. The contents of this work contain five parts:(1) Recent development, application and prospect for Schiff base complexes were reviewed, and the reduction of Schiff base were also discussed.(2) In this paper, sodium borohydride were used as a reducing agent, and two bis-Schiff base:N1-(4-hydroxy-3-methoxylbenzylidene)-N2-(2-(4-hydroxy-3-methoxybenzylidene)ethyl)-1,2-ethylenediamine (Schiff base 1)and N1-(4-hydroxylbenzylidene)-N2- (2-(4-hydroxylbenzylidene)ethyl)-1,2-ethylenediamine(Schiff base 2), were selected and reducted by NaBH4. After reduction, two new nitrogenous compounds were obtained: N1-(4-hydroxy-3-methoxylbenzyl)-N~2-(2-(4-hydroxy-3-methoxylbenzyl)ethyl)-1,2-ethylene ammonium salt (L1·3HCl)and the N~1-(4-hydroxylbenzyl)-N~2-(2-(4-hydroxylbenzyl) ethyl)-1,2-ethylene ammonium salt (L2·3HCl). They were characterized by elemental analysis, IR spectra, 1H NMR, MS and UV-vis. The protonation constants of reductive products and the stability constants their complexes with Cu(Ⅱ) were determined, the equilibrium constants were determined with the program BEST, the species distribution diagrams were obtained with the programs Repro40 and Repro.(3) The Ni(Ⅱ), Cu(Ⅱ) complexes of N,N’-bis-(2-hydroxyl-benzyl)- triethylenetetramine, which were characterized by elemental analysis, X-ray single crystal diffraction analysis, the accurate structure of the complex were determined and the property of them were inferred preliminarily.(4) A bis-Schiff base ligand was obtained by the condensation of salicylaldehyde and triethylenetetramine of a 3:1 ratio, three dinuclear complexes with transition metal (Ni, Cu, Zn) of this ligand were synthesized, they were characterized by elemental analysis, IR spectra, 1H NMR, and X-ray single crystal diffraction analysis, while their fluorescent property were determined at room temperature, results showed that: copper and nickel complexes have no fluorescence, while the zinc complex have stronger fluorescence, thus increasing its possibility of application in fluorescent materials. By DFT calculation, the fluorescent property of the ligand and its zinc complex were further understood and the reasons for the change of the fluorescent intensity were explained.(5) At last, the summary for the contents of this paper was discussed, and the prospect for Schiff base complexes and the development of our work were reviewed.更多还原