几种(C^N)PtIIQ型配合物的电子结构和紫外-可见吸收光谱

在B3LYP/LANL2DZ水平上优化了三种(C^N)PtIIQ 型配合物基态的几何结构, 进行了频率计算, 并采用含时密度泛函(TD-DFT)方法结合极化连续体模型(PCM)计算了目标配合物在CH2Cl2溶液中的电子结构和紫外-可见吸收光谱. 计算值与文献报道值相似. 计算结果表明这三种(C^N)PtIIQ型配合物在可见光区都有强度较大而且宽的吸收峰, 它们的最低能量吸收峰的跃迁具有ILCT(配体内部电荷转移)和部分MLCT(金属向配体的电荷转移)的特征, 不同于PtIIQ2型配合物在多数情况下表现出的ILCT的跃迁性质.

Electronic Structures and UV-Vis Spectra of Several (C^N)PtIIQ Type Complexes

Geometry optimizations and frequency calculations of three (C^N)PtIIQtype complexes in the ground state were performed at the level of B3LYP/LANL2DZ, and their absorption properties in dichloromethane (CH2Cl2) media were calculated by using time-dependent density functional theory (TD-DFT) associated with the polarized continuum model (PCM). The optimized structures and calculated absorption spectra were in reasonable agreement with experimental data. All the complexes had relative strong absorption and broad absorption bands in visible region. The lowest-energy absorption bands of (C^N)PtIIQ type complexes exhibited ILCT (intra-ligand charge transfer) mixed with partially MLCT (metal-to-ligand charge transfer) characteristic, and showed different transition mechanisms compared with those of PtIIQ2 type complexes, whose lowest energy absorption bands were usually dominated by ILCT transitions.