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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (8): 841-846. 上一篇    下一篇

研究论文

双核Pt(II)配合物的光谱结构和激发态性质的密度泛函理论研究

张首才1，王嵩2，周欣*,2，张红星2，邵琛3，李传碧*,1   

  1. (1吉林师范大学化学学院 四平 136000)
    (2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 130061)
    (3东北师范大学化学学院 长春 130024)
  • 投稿日期:2007-09-09 修回日期:2007-10-30 发布日期:2008-04-28
  • 通讯作者: 周欣

DFT Studies on the Spectroscopic and Excited-state Properties of Di-nuclear Pt(II) Complexes

ZHANG Shou-Cai1 WANG Song2 ZHOU Xin*,2 ZHANG Hong-Xing2 SHAO Chen3 LI Chuan-Bi*,1   

  1. (1 College of Chemistry, Jilin Normal University, Siping 136000)
    (2 State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130061)
    (3 Department of Chemistry, Northeast Normal University, Changchun 130024)
  • Received:2007-09-09 Revised:2007-10-30 Published:2008-04-28
  • Contact: ZHOU Xin

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采用基于第一性原理的密度泛函理论对单核和双核三联吡啶Pt(II)配合物[Pt(trpy)C≡CH]＋ (1)和[Pt(trpy)C≡ (2)的基态和激发态以及光谱性质进行了系统研究. 结果揭示了双体配合物中Pt—Pt间距离在激发态时明显短于基态时的距离, 而且双体聚合后最低能吸收和发射波长相对单体配合物发生了明显红移, 这种激发的本质被指认为是来自于[dσ*(dδ*π*)]的MMLCT (metal-to-metal-to-ligand charge transfer)电荷转移跃迁. 另外, 对研究的配合物, 用VWN (Vosko-Wilk-Nusair)泛函优化得到的几何和用SAOP(轨道势的统计平均)计算的光谱能量和实验值符合得很好, 能够准确反映实验现象.

关键词: 双核发光铂(II)配合物, 激发态, 电荷转移跃迁, 密度泛函

The ground and excited states of mono- and di-nuclear terpyridyl Pt(II) complexes [Pt(trpy)C≡CH]＋ (1) and [Pt(trpy)C≡CH] (2) were explored by using the first principle based on a DFT method. The results show that the Pt—Pt bond length is obviously shortened in the excited state relative to that in the ground state and the wavelength of the lowest-energy absorption and emission for the dimer is red-shifted compared with the monomer. The origin of the excitation was attributed to the [dσ*(dδ*π*)] charge transfer transition. In addition, the calculations show that, for the complexes investigated in this work, the optimized geometries by the VWN (Vosko-Wilk-Nusair) functional and spectroscopic energy by the SAOP (statistical average of orbital potentials) functional are in agreement with the experimental values.

Key words: di-nuclear luminescent Pt(II) complex, excited state, charge transfer transition, density functional theory