两种金属钌配合物异构体紫外-可见吸收光谱的理论计算

在B3LYP/LANL2DZ水平上优化了(trpy)(pic)RuCl] (pic是皮考林离子; trpy为2,2’,2"-联三吡啶)顺反两种异构体的结构, 并用含时密度泛函方法(TD-DFT)计算了它们在乙腈溶液中的吸收光谱. 计算表明它们在可见光区都有较强的宽吸收带, 它们在可见光区吸收峰的位置分别为510.2和383.2, 522.5和398.4 nm处, 计算和实验结果在吸收峰的位置和相对强度上都是非常吻合的. 两种异构体的最低能量吸收带都具有MLCT/ILCT/LLCT性质, 在它们的配体上引入—COOH等极性基团则可能用于太阳光伏电池的光敏化剂.

Theoretical Calculation on UV-Vis Spectra of Two Ruthenium-Containing Complex Isomers

Molecular structures of trans-(trpy)(pic)RuCl] and cis-(trpy)(pic)RuCl] were optimized at the level of B3LYP/LANL2DZ, and their absorption spectra in acetonitrile were investigated by using time-dependent density functional method. Calculation results indicate that both of the two isomers have broad and relative strong absorption bands in visible region. Calculated positions of absorption peaks in the visible region for the cis- and trans- isomers are at 510.2 and 383.2, 522.5 and 398.4 nm respectively, the positions and relative strength are in good agreeement with experimental results, and the lowest-energy absorption bands of the two isomers display MLCT/ILCT/LLCT character. It can be predicted that after adjoining polar groups such as —COOH etc on ligand trpy, the two isomers may be used as sensitizers in solar cells.