【作者】 苟丽宁；

【导师】 郭栋才；

【作者基本信息】 湖南大学 ， 化学工艺， 2010， 硕士

【摘要】 酰胺类化合物具有合成简单、结构多变及配位末端基可调等特性,对稀土离子有较好的识别配位能力,本文通过改变配体末端基官能团设计合成出了13种新的苯甲酰胺衍生物以及10种结构新颖并具有良好荧光性能的稀土有机配合物。其研究工作分为以下四个部分：(1)以苯甲酰胺为基本骨架,合成了6种新的含有酯基的苯甲酰胺衍生物[N-苄基-2-(取代酰氧基)苯甲酰胺],通过核磁氢谱、质谱、元素分析及红外光谱等分析手段对目标化合物及其中间体进行了结构表征。(2)以所合成的N-苄基-2-(取代酰氧基)苯甲酰胺为配体,Eu(Ⅲ)为中心离子,合成了6种新的铕-N-苄基-2-(取代酰氧基)苯甲酰胺荧光配合物。通过EDTA配位滴定分析、摩尔电导、元素分析、红外光谱、紫外光谱及热分析等手段确定了目标配合物的结构和组成；采用荧光光谱仪研究了目标配合物的荧光性能。实验结果表明：6种含酯基的化合物N-苄基-2-(取代酰氧基)苯甲酰胺能够与铕离子形成稳定的配合物,铕-N-苄基-2-(苯甲酰氧基)苯甲酰胺、铕-N-苄基-2-(对甲基苯甲酰氧基)苯甲酰胺、铕-N-苄基-2-(对氯苯甲酰氧基)苯甲酰胺、铕-N-苄基-2-(对甲氧基苯甲酰氧基)苯甲酰胺及铕-N-苄基-2-(间氯苯甲酰氧基)苯甲酰胺等5种配合物发出了铕离子的红色特征荧光,单色性好,荧光强度大；铕-N-苄基-2-(苯乙酰氧基)苯甲酰胺配合物发出了配体N-苄基-2-(苯乙酰氧基)苯甲酰胺的绿色荧光,研究表明配合物的结构差别导致了配合物荧光颜色的不同。(3)以苯甲酰胺为基本骨架,合成了7种新的含有亚氨基的苯甲酰胺衍生物[N-苄基-2-(芳基亚氨基氨甲酰基甲氧基)苯甲酰胺],通过核磁氢谱、质谱、元素分析及红外光谱等分析手段对目标化合物及其中间体进行了结构表征。(4)以所合成的N-苄基-2-(芳基亚氨基氨甲酰基甲氧基)苯甲酰胺为配体,Eu(Ⅲ)为中心离子,合成了4种新的铕-N-苄基-2-(芳基亚氨基氨甲酰基甲氧基)苯甲酰胺荧光配合物。7种含亚氨基的化合物中只有N-苄基-2-(间硝基苯亚氨基氨甲酰基甲氧基)苯甲酰胺、N-苄基-2-(对甲氧基苯亚氨基氨甲酰基甲氧基)苯甲酰胺、N-苄基-2-(对羟基苯亚氨基氨甲酰基甲氧基)苯甲酰胺、N-苄基-2-(苯亚氨基氨甲酰基甲氧基)苯甲酰胺等4种能够与中心铕离子形成稳定的配合物,荧光光谱分析结果表明4种配合物所发出的荧光为配体荧光,铕离子的微扰使得配体的发光强度增加。更多还原

【Abstract】 With unusual characteristics of simple synthesitic methods, changeable structures and adjustable terminal groups, amide ligands have high selectivety and good regulatory to lanthanide ions. Thirteen new benzamide derivatives and ten complexes with novel structure and excellent luminescent properties have been synthesized in this paper. This work contains four parts as follows:(1) Six new compounds N-benzyl-2-(substituted acyloxy)benzamide with esters have been synthesized with benzamide as the basic framework. All benzamide derivatives and their intermediates have been characterized by 1H NMR, MS, elemental analysis and FT-IR spectrum.(2) Six new fluorescence complexes of Europium with the ligands of N-benzyl-2-(substituted acyloxy)benzamides have been synthesized. Molecular compositions and strctures were characterized with EDTA titrimetric methods, molar conductance analysis, elemental analysis, FT-IR and UV spectrum analysis, thermal analysis and so on. The luminescence properties of the complexes have also been investigated. Results showed that the ligands with ester group have high selectivety and coordinations to europium ions. The complexes Eu-N-benzyl-2-(benzoyloxy)benzamide, Eu-N-benzyl-2-(p-methyl-benzoyloxy)benzamide, Eu-N-benzyl-2-(p-chloro-benzoyloxy) benzamide, Eu-N-benzyl-2-(p-methoxyl-benzoyloxy)benzamide, Eu-N-benzyl-2-(3-chloro-benzoyloxy)benzamide showed red fluorescence with good single properties and high luminescence intensities. And another complex Eu-N-benzyl-2-(phenyl-acetoxy)benzamide showed green fluorescence which was emittde by N-benzyl-2-(phenyl-acetoxy)benzamide. This study showed that the difference among the complexes leads to the different color of the luminescence properties.(3) Seven new compounds with imino groups have been synthesized with benzamide as the basic framework. All benzamide derivatives and their intermediates have been characterized by 1H NMR, MS, elemental analysis and FT-IR spectrum.(4) Four new fluorescence complexes of Europium with the ligands N-benzyl-2-(aryliminocarbamoylmethoxy)benzamide have been synthesized. Their molecular compositions and strctures were characterized by EDTA titrimetric methods, molar conductance analysis, elemental analysis, FT-IR and UV spectrum analysis, thermal studies and so on. The luminescence properties of the comlexes have also been investigated. Results showed that four complexes with ligands N-benzyl- 2-(3-nitro-benzyliminocarbamoylmethoxy)benzamide, N-benzyl-2-(4-methoxyl-ben zyliminocarbamoylmethoxy)benzamide,N-benzyl-2-(4-hydrox-yl-benzyliminocarb-amoylmethoxy)benzamide, N-benzyl-2-(benzyliminoarbamoylmethoxy)benzamide possess excellent stabilities. And the flourescence spectucm results showed that they all admitted the flourescence of the ligands. It is Europium who enhanced the luminescence intensity of ligands.更多还原