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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (16): 1681-1687. 上一篇    下一篇

研究论文

三核金配合物分子间Au-Au相互作用及其发光性质的含时密度泛函理论研究

张明昕*, 吴克琛, 莽朝永   

  1. (中国科学院福建物质结构研究所 结构化学国家重点实验室 福州 350002)
  • 投稿日期:2005-11-04 修回日期:2006-04-27 发布日期:2006-08-28
  • 通讯作者: 张明昕

Luminescent Properties and Intermolecular Au…Au Interactions of Trinuclear Gold(I) Complexes Studied by TD-DFT Method

ZHANG Ming-Xin*; WU Ke-Chen; MANG Chao-Yong   

  1. (State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002)
  • Received:2005-11-04 Revised:2006-04-27 Published:2006-08-28
  • Contact: ZHANG Ming-Xin

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被引次数

5 | 1

使用混合密度泛函方法(MPW1PW91交换相关势), 对Au3(HOC＝NH)3分子进行了几何构型全优化, 在此基础上构建了Au3(HOC＝NH)3二聚体和三聚体模型, 采用含时密度泛函方法研究了单体和低聚体模型的分子间Au-Au相互作用与其发光性质的关系. 计算结果表明: 此d10亚金化合物低能激发态的主要成分是反键或非键的Au(5d)电子轨道到前线附近Au(6p)空轨道的跃迁, 并且这种激发大大加强了分子间Au-Au相互作用, 从而形成激发多聚体, 导致这类化合物溶液或固体发射谱红移.

关键词: 金低聚体, 发光, 含时密度泛函理论, 分子间作用

A full optimization on the ground-state geometry of the trinuclear gold(I) organometallic complex, Au3(HN＝COH)3, was carried out at MPW1PW/SDD level. Some models of dimer and trimer of Au3(HN＝COH)3 were set up basing on the optimized ground-state structure of the monomer. The luminescent properties and the intermolecular interactions of the oligomers of Au3(HN＝COH)3 were studied by TD-DFT (time-dependent density functional theory) method. The results showed that the intermolecular aurophilic effects, which resulted in exciplexes, were strongly enhanced in the excited states and led to the huge red-shifts of the optical absorption and emission spectra. It also showed that the low energy transitions of these trigold complexes come mainly from occupied Au(5d) orbitals to vacant Au(6p) orbitals.

Key words: gold(I) oligomer, luminescence, time-dependent density functional theory, intermolecular interaction