高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

[Au(PH3)]+修饰下苯的激发态性质的理论研究

矫玉秋1, 潘清江1,2, 张红星1   

    1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130021;
    2. 黑龙江大学化学化工与材料学院, 哈尔滨 150080
  • 收稿日期:2005-06-02 修回日期:1900-01-01 出版日期:2008-02-10 发布日期:2008-02-10
  • 通讯作者: 张红星

Theoretical Study of Excited States Properties of Phenyl Modified [Au(PH3)]+

JIAO Yu-Qiu1, PAN Qing-Jiang1,2, ZHANG Hong-Xing1*   

    1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130021, China;
    2. School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China
  • Received:2005-06-02 Revised:1900-01-01 Online:2008-02-10 Published:2008-02-10
  • Contact: ZHANG Hong-Xing

PDF (PC)

摘要： 用MP2和CIS方法分别优化了H3PAuPh(a)、对位(H3PAu)2C6H4(b)和间位(H3PAu)3C6H3(c)的基态和激发态结构. 计算结果表明, [Au(PH3)]+的引入使Au(Ⅰ)配合物的苯环上的电子云密度降低, 削弱了苯基内C—C键的成键作用. 计算得到配合物a~c的最低能量磷光发射分别为443, 461和429 nm, 均属于苯基为π*→π跃迁本质, 并伴有Au(6p)→π(Ph)和Au(6p)→Au(5d)电荷转移性质. 与苯的最低能量磷光发射(413 nm)相比揭示了配合物a~c的发光过程是[Au(PH3)]+修饰的π*→π发光机制.

关键词: 激发态, 磷光, 从头计算, Au(Ⅰ)配合物

Abstract: The structures in ground and lowest-energy triplet excited states for [Au(PH3)]C6H5(a), 1,4-bi(AuPH3)-C6H4(b) and 1,3,5-ter(AuPH3)-C6H3(c) were optimized by the MP2 and CIS methods, respectively. It was shown that the introduction of [Au(PH3)]+ decreases the electron density around phenyl ring, which weakens the C—C bonding in the ring. The lowest-energy phosphorescences of a—c were predicted at 442.7, 461.3 and 428.9 nm by the CIS method, respectively. Comparison with that of benzene shows that the phosphorescent emissions of a—c exhibit the π*→π transition involved in the phenyl ring, accompanied by Au(6p)→Ph and Au(6p)→Au(5d) charge transfer transitions.

Key words: Excited state, Phosphorescence, Ab initio, Au(Ⅰ) complex

中图分类号: 

TrendMD: