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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (22): 2665-2672. 上一篇    下一篇

研究论文

C^N^NPt(II)及N^C^NPt(II)配合物二阶非线性光学性质的DFT研究

刘艳，孙世玲，孙秀欣，刘春光，仇永清*   

  1. (东北师范大学化学学院 功能材料化学研究所 长春 130024)
  • 投稿日期:2011-05-09 修回日期:2011-07-15 发布日期:2011-07-20
  • 通讯作者: 仇永清 E-mail:qiuyq466@nenu.edu.cn
  • 基金资助:

    自然科学基金;吉林省自然科学基金

DFT Study on Second-order Nonlinear Optical Properties of C^N^NPt(II) and N^C^NPt(II) Complexes

LIU Yan, SUN Shi-Ling, SUN Xiu-Xin, LIU Chun-Guang, CHOU Yong-Qing   

  1. (Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024)
  • Received:2011-05-09 Revised:2011-07-15 Published:2011-07-20
  • Contact: Qiu Yong-Qing E-mail:qiuyq466@nenu.edu.cn

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采用密度泛函理论(DFT) BHandHYLP方法, 计算分析C^N^N配体, C^N^NPt(II) (C^N^N＝6-苯基-2,2连吡啶)及N^C^NPt(II) (N^C^N＝1,3-二吡啶基-苯)配合物的极化率和二阶非线性光学(NLO)系数. 结果表明形成金属配合物后二阶NLO系数明显增大, 配合物2b的β值是配体Lb的11倍. 增加副配体的共轭性及取代基接受电子的能力都可以提高配合物的二阶NLO系数. TD-BHandHLYP方法计算配合物的电子光谱与实验测定结果相吻合, 配合物C^N^NPt(II) 和N^C^NPt(II)的最大吸收波长是由不同的电子跃迁形式引起的, 取代基对N^C^NPt(II)配合物的最大吸收波长有一定影响, 而对C^N^NPt(II)配合物影响较小.

关键词: Pt(II)配合物, 电子光谱, 二阶NLO系数, DFT

Density functional theory (DFT) with the BHandHLYP functional was employed to investigate the polarizability and second-order nonlinear optical (NLO) coefficients of C^N^N ligands, C^N^NPt(II) (C^N^N＝6-phenyl-2,2-bipyridines) and N^C^NPt(II) (N^C^N＝1,3-di(2-pyridyl)-benzene) complexes. The calculations indicate that the second-order NLO coefficients of complexes are enhanced significantly and the β value of complex 2b is about 11 times as large as that of ligand Lb. In addition, the second-order NLO coefficients of complexes are also enhanced by increasing the conjugation of ancillary ligands and the electron-withdrawing ability of substituents. The electronic spectra of complexes were analyzed by the time-dependent density function theory (TD-BHandHLYP) method. The results show that the experimental absorption spectra are well reproduced by the theoretical data. The maximum absorptions of C^N^NPt(II) and N^C^NPt(II) complexes are assigned to different kinds of electronic transitions. And the substituents have larger effects on the maximum absorptions of N^C^NPt(II) complexes, while less effects on that of C^N^NPt(II) complexes.

Key words: Pt(II) complex, electronic spectra, second-order NLO coefficients, DFT