【摘要】 应用MP2和CIS方法分别优化了IrR(CO)(PH3)2(mnt)[mnt=maleonitriledithiolate;R=H(1),CH3(2),Br(3)]系列配合物的基态和激发态几何结构.使用TD-DFT方法计算了配合物的吸收和发射光谱.计算结果表明:配合物1～3在430,435及439nm处的最低能吸收均为ILCT/LLCT/MLCT混合跃迁性质,它们的最低能磷光发射和吸收性质相似,发射波长则红移至760,770和800nm.配合物2与1的几何结构、光谱性质都很接近,而配合物3中,由于溴的引入使其基态和激发态几何构型及前线分子轨道成分与1和2有很大不同,进而对其光谱及跃迁性质产生了影响.更多还原

【Abstract】 MP2 and CIS methods were used to optimize the ground- and excited-state structures of IrR(CO)(PH3)2(mnt) complexes [mnt=maleonitriledithiolate; R=H (1), Me (2), and Br (3)]. The absorption and emission spectra were calculated using a TD-DFT method. The calculated results indicated that the lowest-energy absorptions of 1～3 at 430, 435 and 439 nm were all the admixture of the ILCT/LLCT/MLCT transitions. The emissions were red-shifted to 760, 770 and 800 nm, the origins of which are similar to those of the lowest-energy absorptions. The structure and spectroscopic properties of 2 and 1 are close with each other, but the introduction of Br for 3 changes the ground- and excited-state geometries and the compositions of frontier orbitals, which affects the emission spectra and transition characters.更多还原