锰、铁、钴氮杂金属冠醚的红外和紫外光谱研究  

Studies on Infrared and UV-vis Spectra of Azametallacrown Complexes Containing Mn(Ⅲ), Fe(Ⅲ) or Co(Ⅲ)

作　　者：林深[1] 刘世雄[1] 

机构地区：[1]福州大学化学系

出　　处：《光谱学与光谱分析》2002年第6期959-962,共4页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金 (No 2 9771 0 0 7);福建省自然科学基金 (No E0 0 1 0 0 1 8)

摘　　要：本文报导了含铁、钴、锰氮杂金属冠醚及其配体的红外和紫外光谱研究结果。对 4 0 0～ 4 0 0 0cm- 1 范围的主要红外吸收谱峰进行了经验归属 ,并进一步讨论了合成的配体和配合物的特征吸收谱带与其结构的关系。配体IR谱中的ν(CO) ,ν(NH) ,δ(NH) +ν(CN) ,δ(NH)等酮式特征吸收在配合物的IR谱图中基本消失 ,～ 16 0 0cm- 1 处出现归属于共轭体系CNNC骨架伸缩振动的吸收谱带 ,～ 15 6 0和～ 14 10cm- 1 附近各出现一尖锐的强吸收 ,他们分别归属于ν(CO)和ν(CO) ,说明该系列N 烷酰基水杨酰肼配体固态时主要以酮式存在 ,在溶液中则先异构为烯醇式结构 ,然后醇羟基再通过去质子化作用使羟氧与金属配合。电子光谱研究结果表明该系列配合物出现苯环及共轭体系的π～π 或n～π 的跃迁 (～ 2 0 4和 2 2 0～2 5 6nm)、M L荷移跃迁带 (2 74～ 35 0nm)和在配位体场作用下金属原子的d d跃迁吸收峰 (～ 5 0 0nm)。IR and UV vis spectral properties of azametallacrown complexes containing Mn(Ⅲ), Fe(Ⅲ) or Co(Ⅲ) were investigated. The relation between the main IR bands in 400-4 000 cm -1 and the structure of azametallacrown complexes were discussed. The absorption bands of ν (C O) , ν (NH), δ (NH)+ ν (CN) and δ (NH) which existed in the IR spectra of the ligands disappeared in the IR spectra of the complexes. A strong band found at -1 600 cm -1 is assigned to C[ZJZS;ZX;LX,Y] NNC group. Bands at ～1 560 cm -1 and -1 410 cm -1 are attributed to ν (C N) and ν (CO), respectively. These results suggest that the ligands in solid state may exit as keto form, and the ligands in the solution may first undergo isomerization to enol form and then coordinated to metal centers through deprotonation. The bands found at -204 and 220-256 nm can be assigned to π π  or n π  transitions of the π conjugation in C[ZJZS;ZX;LX,Y] NNC framwork and benzene ring. The absorption maxima at 274-350 nm could be assigned to metal to ligand charge transfer (MLCT) transition. The d d transition band for the metal atoms was observed at -500 nm.

关 键 词：锰 铁 钴 氮杂金属冠醚 红外光谱 紫外可见光谱 超分子化合物 多核金属配合物 结构 

分 类 号：O623.423[理学—有机化学] O64[理学—化学]