高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (12): 1908.

• 论文 • 上一篇    下一篇

双核铂配合物Pt2(CN)4(CNC4H9)4的发光机制及Pt…Pt间相互作用的从头计算研究

杨光辉1, 张红星1, 王悦2, 唐敖庆1   

  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;
    2. 教育部超分子结构与谱学开放实验室, 长春 130023
  • 收稿日期:2000-05-31 出版日期:2000-12-24 发布日期:2000-12-24
  • 通讯作者: 张红星(1963年出生),男,博士,教授,从事量子化学研究.
  • 基金资助:

    国家自然科学基金(批准号:29892168)资助

An ab initio Study of the Luminescence and the Pt(Ⅱ)…Pt(Ⅱ) Interaction in the Compound Pt2(CN)4(CNC4H9)4

YANG Guang-Hui1, ZHANG Hong-Xing1, WANG Yue2, TANG Au-Qing1   

  1. 1. State Key Laboratory of Theoreticaland Computational Chemistry;
    2. Key Laboratory for Supr amolecular Structure and Spectra, Instituteof Theoretical Chemistry Jilin University, Changchun 130023, China
  • Received:2000-05-31 Online:2000-12-24 Published:2000-12-24

摘要: 利用从头算MP2方法优化了Pt(CN)2(CNCH3)2,Pt(CN)2(CNCH3)2-(NCCH3)2.[Pt(CN)2·(CNCH3)2]2的基态几何结构;利用单激发的组态相互作用方法(CIS)计算了固态和乙氰溶液中标题化合物的发射光谱,并对激发态的几何结构进行了优化.结果表明:基态时,Pt…NCCH3之间的距离较大(0.406nm),说明溶剂分子与Pt原子之间存在较小的范德华作用;而激发态时,Pt…NCCH3之间的距离减小(0.257nm),说明此时Pt…NCCH3之间相互作用较强,由于这种作用使乙氰溶液中该物质的发光性质与不考虑溶剂效应时相比差异较大.其发射光谱不在可见光谱区.固态时,此化合物为直线链状结构.MP2计算得到:基态时[Pt(CN)2(CNCH3)2]2中Pt…Pt之间的距离为0.339nm,电荷布居为0.032.说明Pt…Pt间有一定的成键性质,这种相互作用促使形成二聚体,并影响其固态的发光性质.其发射光谱在可见光谱区内

关键词: Pt2(CN)4(CNC4H9)4, 从头计算, 发光机制, 发射光谱

Abstract: The Optimizations on the ground state structures were performed under the MP2calculations for Pt(CN)2(CNCH3)2, Pt(CN)2(CNCH3)2-(NCCH3)2and [Pt(CN)2(CNCH3)2]2. Based on these calculations, single excitation configuration interaction (CIS) calculations were carried out to optimize the molecular structures of the excited states and to reveal the excited state electronic structures.The MP2calculations showed that the Pt(Ⅱ)…NCCH3distance are0.405 2 nm in ground state 1Agof Pt(CN)2(CNCH3)2-(NCCH3)2, indicating that CH3CNmolecule is weakly interactive with Pt in the ground state.However, the distance became0.028 10 nm in the excited state, suggestion of a rather strong interaction between Pt(CN)2(CNCH3)2and the solvent molecule in the NCCH3solution.The complex is a linear chain structure at solid state with the Pt(Ⅱ)…Pt(Ⅱ) distance of0.033 25 nm, which illustrated a typical d8-d8attraction in Pt(Ⅱ) complexes.Therefore, the solvation and the metal-metal interaction significantly affect the luminescence of the Pt(CN)2(CNC4H9)2complex in the NCCH3solution and in solid state respectively

Key words: Pt2(CN)4(CNC4H9)4, ab initio, Luminescence, Emission spectra

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