物理化学学报 >> 2011, Vol. 27 >> Issue (02): 302-308.doi: 10.3866/PKU.WHXB20110223

理论与计算化学 上一篇    下一篇

8-羟基喹啉银(铂)金属配合物电子光谱与非线性光学性质

卫航, 张荣红, 袁波, 杨帆, 李权, 赵可清   

  1. 四川师范大学化学与材料科学学院, 先进功能材料四川省高校重点实验室, 成都 610066
  • 收稿日期:2010-07-23 修回日期:2010-11-15 发布日期:2011-01-25
  • 通讯作者: 李权 E-mail:liquan6688@163.com
  • 基金资助:

    国家自然科学基金(50973076), 四川省科技计划项目(2010JY0041)和四川师范大学科研经费(09ZDL03)资助

Electronic Spectra and Nonlinear Optical Properties of 8-Hydroxyquinolinolate-Ag (Pt) Metal Complexes

WEI Hang, ZHANG Rong-Hong, YUAN Bo, YANG Fan, LI Quan, ZHAO Ke-Qing   

  1. Key Laboratory of Advanced Functional Materials, Sichuan Province Higher Education System, College of Chemistry and Material Science, Sichuan Normal University, Chengdu 610066, P. R. China
  • Received:2010-07-23 Revised:2010-11-15 Published:2011-01-25
  • Contact: LI Quan E-mail:liquan6688@163.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (50973076), Science and Technology Plan of Sichuan Province, China (2010JY0041), and Science Research Fund of Sichuan Normal University, China (09ZDL03).

摘要:

运用密度泛函理论B3LYP方法对8-羟基喹啉(银、铂)(AgQ、PtQ2)金属配合物及其衍生物的非线性光学性质进行理论计算研究. 结果表明: 引入取代基使铂配合物的最强吸收波长产生较大红移. 最低能量跃迁吸收来自最高占据分子轨道(HOMO)到最低空分子轨道(LUMO)的d→π*π→π*跃迁, 属于金属配体电荷转移(MLCT)与配体配体电荷转移(LLCT). 金属银和铂掺杂8-羟基喹啉使其三阶非线性光学系数γ值明显增大, 并且在配合物上引入―Ph, ―PhOCH3, ―PhF2, ―PhF5基团将进一步增大γ值. 引入基团的供电子性越强, γ值增大的幅度越大, 引入基团的吸电子性越强, γ值增大的幅度越小.

关键词: 密度泛函理论, 8-羟基喹啉, 金属配合物, 非线性光学性质, 电子光谱

Abstract:

Density functional theory with the B3LYP level was used to investigate the nonlinear optical properties of 8-hydroxyquinolinolate (Ag, Pt)(AgQ, PtQ2) metal complexes and their derivatives. The introduction of substituents resulted in considerable red shifts for the highest absorption wavelength of the Pt complexes. The lowest energy excitation absorption mainly consisted of d→π* and π→π* excitations from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). Metal to ligand charge-transfer (MLCT) and ligand to ligand charge-transfer (LLCT) were mainly involved. Adulteration with the transition metals Pt and Ag resulted in a significant increase in the third-order nonlinear optical coefficient γ of 8-hydroxyquinolinolate. The introduction of ―Ph, ―PhOCH3, ―PhF2, and ―PhF5 further improved the γ value of the 8-hydroxyquinolinolate metal complexes. The gradient of the γ value increased with an increase in the electron-donating ability of the introduced substituent. This gradient was lower for substituent with a higher electron-accepting ability.

Key words: Density functional theory, 8-Hydroxyquinolinolate, Metal complexes, Nonlinear optical property, Electronic spectrum

MSC2000: 

  • O641