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  

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

作　　者：张明昕[1] 吴克琛[1] 莽朝永[1] 

机构地区：[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

出　　处：《化学学报》2006年第16期1681-1687,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.90203017;20573114);国家973基础研究(No.2004CB720605);福建省青年创新基金(No.2003J043)资助项目.

摘　　要：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.A full optimization on the ground-state geometry of the trinuclear gold（I） organometaUic 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.

关 键 词：金低聚体 发光 含时密度泛函理论 分子间作用 

分 类 号：O641.4[理学—物理化学]