双核镉配聚物及其衍生物荧光光谱的密度泛函理论研究

A DFT study of the luminescence spectrum properties of metal Cd complex and its derivatives

采用DFT-B3LYP/6-31+G(d)方法,对配聚物[Cd2Cl4(Hbm)2]及其6种衍生物([M2-Cl4(HbmL)2],M=Zn2+,Hg2+;L=—CH3;—NH2;—CN)基态结构进行优化,用TD-DFT/B3LYP/6-31+G(d)方法计算其吸收光谱;同时用HF-CIS/6-31G(d)方法优化其最低激发单重态的几何结构,用含时密度泛函理论计算发射光谱.结果表明:电子在基态与激发态间的跃迁,主要是在卤素配体Cl到金属离子M的电荷转移(LMCL);发射光谱峰的计算最大值与实验值基本符合.改变中心金属离子M和咪唑环上的5位取代基可以精细地调控发光材料的光谱波段.

The frontier molecular orbits and electronic spectrum of Cd complex 1 for [Cd2Cl4（Hbm）2] and its derivates（[M2Cl4（HbmL）2],M=Zn2＋,Hg2＋;L=—CH3;—NH2;—CN） are calculated by CIS and TD-DFT methods at the B3LYP/6-31＋G（d） level.The effects of substituting group on the EL emission peak with TD-B3LYP/6-31＋[KG-＊6]G（d） method were analyzed.The calculated results indicated that the luminescence originates from the electronic transition from the Cl to the M.The calculated results of the emission spectrum for Cd complex have good agreement with the experimental data.All compounds are excellent electron transporting materials,luminescence wave bands of which can be tuned by different metals and substituent on the ligand.