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采用自旋限制和非限制B3LYP/UB3LYP方法分别优化了系列Os(Ⅱ)二亚胺配合物[Os(L)2(CN)2(phen)][phen=1,10-邻二氮杂菲;L=PH3(1),二甲基亚砜(DMSO)(2)]及[Os(PH3)2(phen)Br2](3)的基态和激发态几何构型.通过TD-DFT方法结合PCM溶剂化模型计算了配合物1～3在二氯甲烷溶液中的吸收和发射光谱并指认了相应的跃迁性质.通过理论化学计算,揭示了π酸配体及π碱配体对配合物磷光发射性质的影响及原因.并进一步解释了配合物3易于在Os—Br键处断裂而发生反应的量子化学机理.对配合物在不同溶剂中的磷光发射性质的计算表明,溶剂对配合物的量子产率存在着影响并且配合物具有溶剂化显色效应。
A series of Os (Ⅱ) diimine complexes [Os (L) 2 (CN) 2 (phen)] [phen = 1, 10-phenanthroline was optimized by using spin-restricted and unrestricted B3LYP / UB3LYP methods, ; The ground state and excited state geometries of L = PH3 (1), DMSO (2)] and [Os (PH3) 2 (phen) Br2] PCM solvation model was used to calculate the absorption and emission spectra of the complexes 1 to 3 in dichloromethane and to identify the corresponding transition properties.The theoretical calculations revealed that the π acid ligands and the π base ligands have a good effect on the complex phosphorescence The nature and nature of the emission properties and further explains the quantum chemistry of the complex 3 that readily undergoes cleavage at the Os-Br bond.The calculation of the phosphorescent emission properties of the complexes in different solvents shows that the effect of the solvent on the complex The quantum yield has an impact and the complex has a solvatochromic effect.