含多个氧化还原中心的卟啉化合物的电化学及光谱电化学行为（Ⅰ）  

Electrochemical and Spectroelectrochemical Behaviour of Porphyrin Compounds Containing Several Redox Centres(Ⅰ)

作　　者：陶建中[1] 孙浩然[1] 师同顺[1] 曹锡章 

机构地区：[1]吉林大学化学系,河南技术师范学院

出　　处：《高等学校化学学报》1994年第11期1657-1661,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：在ＤＭＦ及ＤＭＳＯ中用循环伏安法、现场紫外可见光谱电化学方法及现场ＦＴ－ＩＲ光谱电化学方法研究了含多个氧化还原中心的卟啉化合物［四（对－硝基苯基）卟啉合钴（Ⅱ）］的氧化还原性质。指出该化合物的第一步氧化或第一步还原为中心金属钴失去或得到１个电子；第二步还原为卟啉环ｍｅｓｏ位的４个对硝基苯基上的硝基在同一电位下各得１个电子，形成相应的阴离子自由基；第三步还原为卟啉环得到１个电子，但该步反应不可逆。同时发现硝基与卟啉环及中心金属钴之间存在分子内电子相互作用，而４个硝基取代基之间未发现分子内电子相互作用。The redox behaviour of porphyrin compounds containing several redox centres(where the porphyrin compound is meso-tetrakis (4-nitrophenyl)-porphyrinatocobalt(Ⅱ),[TNPPCo(Ⅱ)]) was investigated by cyclic voltammetry,in-situ UV-visible and FT-IR spectroelectrochemistry in dimethylformamide(DMF)and dimethylsulfoxide(DMSO).The first oxidation or reduction of TNPPCo(Ⅱ)is that centre metal cobalt(Ⅱ)loses or obtains one electron and leads to the formation of[TNPPCo(Ⅲ)]+ or [TNPPCo(I)]-.The secondreduction of TNPPCo(Ⅱ) is that four nitro groups of nitrophenyl on porphyrin ring meso sites respectively obtain one electron at the same potential and lead to the formation of the corresponding radical anions, and in this step overall porphyrin molecule obtains four electrons and leads to the formation of[TNPPCo(I)]5-.The third reduction of TNPPCo(Ⅱ) is that the porphyrin ring obtains one electron, but this reaction is irreversible. It was found that the intermolecular electronic interaction occured between nitro groups and porphyrin ring or centre metal cobalt,but the intermolecular electronic interaction among four nitro groups was not found.

关 键 词：卟啉化合物 电化学 光谱 氧化还原 

分 类 号：O626.323[理学—有机化学]