高等学校化学学报

高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (12): 2791.doi: 10.7503/cjcu20130685

• 物理化学 • 上一篇    下一篇

12顶点[1-R-CB11-Me11]-碳硼烷氧化-还原过程二阶NLO效应的理论研究

王娇1, 张梦颖1, 邹海艳1, 于海玲2, 王文勇1, 宋红娟1, 李晓倩1, 仇永清1   

  1. 1. 东北师范大学化学学院, 功能材料化学研究所, 长春 130024;
    2. 吉林农业大学资源与环境学院, 长春 130118
  • 收稿日期:2013-07-19 出版日期:2013-12-10 发布日期:2013-10-23
  • 作者简介:仇永清，男，博士，教授，博士生导师，主要从事应用量子化学研究. E-mail：qiuyq466@nenu.edu.cn
  • 基金资助:

    国家自然科学基金（批准号：21173035）资助.

Theoretical Study on Redox-adjustable Second-order Nonlinear Optical Responses of 12-Vertex [1-R-CB11-Me11]- Carborane Complexes

WANG Jiao1, ZHANG Meng-Ying1, ZOU Hai-Yan1, YU Hai-Ling2, WANG Wen-Yong1, SONG Hong-Juan1, LI Xiao-Qian1, QIU Yong-Qing1   

  1. 1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China;
    2. College of Resources and Environmental Science, Jilin Agricultural University, Changchun 130118, China
  • Received:2013-07-19 Online:2013-12-10 Published:2013-10-23

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摘要：

采用密度泛函理论（DFT）对12顶点[1-R-CB11-Me11]-碳硼烷的结构和二阶非线性光学（NLO）调节效应进行计算分析. 结果表明，C位连接的取代基R供、吸电子能力的不同以及分子发生可逆氧化-还原反应对分子构型有一定影响. 由自然键轨道（NBO）电荷和电子自旋密度分析可知，分子的氧化中心是碳硼笼，分子的氧化反应可导致碳硼笼部分给、受体特性发生改变. 氧化态分子的第一超极化率总有效值（βtot）大于相应还原态分子，当C位取代基R为供电子基团（—NH2）的分子时，氧化态与还原态的βtot值变化最大. 这类分子的氧化-还原反应可以有效调节二阶NLO光学效应.

关键词: 12顶点碳硼烷, 二阶非线性光学效应, 氧化-还原, 密度泛函理论

Abstract:

The second-order nonlinear optical(NLO) properties of 12-vertex [1-R-CB11-Me11]- carborane complexes were investigated with the density functional theory(DFT) method. The results indicate that both the electron-donating or electron-withdrawing substituents and the reversible redox reaction of molecules can affect the molecular geometry. By the force of natural bond orbital(NBO) charge and the electron spin density analysis, we conclude that the molecular oxidation center is in carborane cage. The oxidation reactions of molecules have a significant effect on changing the electronic character of carborane. Meanwhile, the oxidization of the carborane anion is more helpful to enhance the βtot value, for instance the amino derivative of carborane. Therefore, the redox reaction of this carborane can be used to adjust the second-order NLO response effectively.

Key words: 12-Vertex carborane, Second-order nonlinear optical(NLO) response, Redox, Density functional theory

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