高等学校化学学报

高等学校化学学报 ›› 1996, Vol. 17 ›› Issue (12): 1899.

• 论文 • 上一篇    下一篇

推拉电子取代基对二茂铁衍生物性质及电子结构的影响

柴向东, 姜月顺, 杨文胜, 张东, 曹云伟, 诸真家, 李铁津   

  1. 吉林大学化学系, 长春, 130023
  • 收稿日期:1995-12-13 出版日期:1996-12-24 发布日期:1996-12-24
  • 通讯作者: 柴向东,男,34岁,副教授.
  • 作者简介:柴向东,男,34岁,副教授.
  • 基金资助:

    国家自然科学基金

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

CHAI Xiang-Dong, JIANG Yue-Shun, YANG Wen-Sheng, ZHANG Dong, CAO Yun-Wei, ZHU Zhen-Jia, LI Tie-Jin   

  1. Department of Chemistry, Jilin University, Changchun, 130023
  • Received:1995-12-13 Online:1996-12-24 Published:1996-12-24

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被引次数

48

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,E0x1、E0x2分别为0.33、0.59V,第一氧化态PⅡ+(D-Fe+-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→π*CT带,应具有较高的二阶分子极化系数,应当是较好的SHG材料。

关键词: 二茂铁衍生物, 推拉电子取代基, 电子结构, 光谱电化学

Abstract: 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 LMCTand π→π CTbands at 356 and 320 nm, respectively, which should result in high second order nonlinear optical response.

Key words: Ferrocene derivatives, Electronic pushing and drawing substituents, Electronic structures, Spectroelectrochemistry

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