推拉电子取代基对二茂铁衍生物性质及电子结构的影响  

Effect of Electron Pushing and Drawing Substituents on Properties and Electronic Structures of Derivatives

作　　者：柴向东[1] 姜月顺[1] 杨文胜[1] 张东[1] 曹云伟[1] 诸真家[1] 李铁津 

机构地区：[1]吉林大学化学系

出　　处：《高等学校化学学报》1996年第12期1890-1903,共14页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金

摘　　要：根据前线轨道理论分析３种具有推拉电子取代基的二茂铁衍生物循环伏安曲线、电子吸收光谱及光谱电化学行为，并给出了分子轨道能级图，实验结果表明，ＰⅡ有两对可逆氧化还原峰，Ｅ１、Ｅ２分别为０．３３、０．５９Ｖ，第一氧化态ＰⅡ＋￣（Ｄ—Ｆｃ￣＋—Ｒ）在６１３ｎｍ有强的ＬＭＣＴ（ｌｉｇａｎｄ－ｔｏ－ｍｅｔａｌ－ｃｈａｒｇｅ－ｔｒａｎｓｆｅｒ）带，是一种良好的光学特性氧化还原开关．ＰⅡ在３５４ｎｍ处出现强的ＬＭＣＴ带，ＰⅢ在３５６ｎｍ和３２０ｎｍ处分别出现强的ＬＭＣＴ和π→πＣＴ带，应具有较高的二阶分子极化系数，应当是较好的ＳＨＧ材料．Three ferrocene derivatives were synthesized and their results of cyclic voltammetry,electronic absorption spectra and spectroelectrochemistry were analyzed in terms of frontier molecular orbital interactions. Their molecular orbital energy levels were given on the basis of the analysis. Experimental results show that PⅡ has two reversible redox couples,the corresponding values of and are 0.33 and 0.59V,respectively.In the first oxidation state,PⅡ+(D-Fc+-R) shows a strong LMCT (ligand-to-metal-charge-transfer)band at 613 nm.This suggests that it may serve as a redox switching of optical properties.PⅢ shows strong LMCT and π→π CT bands at 356 and 320 nm, respectively, which should result in high second order nonlinear optical response.

关 键 词：二茂铁衍生物 推拉电子取代基 电子结构 光谱 

分 类 号：O627.81[理学—有机化学]