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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (11): 1027-1031. 上一篇    下一篇

研究论文

一系列d8配合物1,3[(dz2)(pz)]激发态和金属间相互作用的理论研究

潘清江1, 郭元茹2, 付宏刚*,1, 张红星3   

  1. (1黑龙江大学化学化工与材料学院 哈尔滨 150080)
    (2东北林业大学材料科学与工程学院 哈尔滨 150040)
    (3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 130023)
  • 投稿日期:2006-07-28 修回日期:2006-11-21 发布日期:2007-06-14
  • 通讯作者: 付宏刚

Theoretical Studies on 1,3[(dz2)(pz)] Excited States and Metal-Metal Interaction of a Series of d8 Complexes

PAN Qing-Jiang1; GUO Yuan-Ru2; FU Hong-Gang*,1; ZHANG Hong-Xing3   

  1. (1 School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080)
    (2 College of Material Science and Engineering, Northeast Forestry Univer-sity, Harbin 150040)
    (3 State Key Laboratory of Theoretical and Computational Chemis-try, Institute of Theoretical Chemistry, Jilin University, Changchun 130023)
  • Received:2006-07-28 Revised:2006-11-21 Published:2007-06-14
  • Contact: FU Hong-Gang

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采用MP2和CIS方法分别优化trans-[M2(CN)4(PH2CH2PH2)2] [M＝Pt (1), Pd (2)和Ni (3)]和trans-[M(CN)2(PH3)2] [M＝Pt (4), Pd (5)和Ni (6)]的基态和1,3[(dz2)(pz)]激发态结构. CIS计算显示1的激发态Pt-Pt距离相对基态变短, 而2和3的金属间距离却增长. TD-DFT方法合理地预测了1～6发射能, 如: 1在CH2Cl2溶液中分别拥有348和404 nm的荧光和磷光发射, 与实验的386和448 nm相对应. 在1～3的激发态中, d8-d8相互作用依次递减, 相应的发射跃迁能增加; 与单核配合物4～6相比, 金属间相互作用使得双核Pt配合物的发射波长红移, 而对双核Pd和Ni配合物影响很小.

关键词: d8配合物, 金属间相互作用, 激发态, 含时密度泛函

The structures of trans-[M2(CN)4(PH2CH2PH2)2] [M＝Pt (1), Pd (2) and Ni (3)] and trans- [M(CN)2(PH3)2] [M＝Pt (4), Pd (5) and Ni (6)] in the ground and 1,3[(dz2)(pz)] excited states were optimized by the MP2 and CIS methods, respectively. The CIS calculations revealed that upon excitation the Pt-Pt distance of 1 shortens but those of 2 and 3 lengthened. Ex-perimental emissions were well reproduced by the TD-DFT calculations. For example, the fluores-cent/phosphorescent emissions of 1 were predicted to take place at 356/417 nm in the solid state and at 348/404 nm in the CH2Cl2 solution, agreeing with experimental 388/450 and 386/448 nm, respectively. It is shown that the metal-metal interaction decreases on going from 1 to 3 in their excited states, leading to the increase of the σ(pz)→σ* (dz2) emission energy along the series complexes. With respect to analogous mononu-clear d8 complexes (4～6), the d8-d8 interaction results in a large red shift of emission wavelength for the binuclear Pt(II) complex but slightly affects those of the binuclear Pd(II) and Ni(II) complexes.

Key words: d8 complex, metal-metal interaction, excited state, TD-DFT