π共轭有机物以及金属铱有机配合物发光性质的研究

【作者】 刘涛；

【导师】 高金胜；

【作者基本信息】 黑龙江大学 ， 有机化学， 2006， 硕士

【摘要】 本文应用量子化学方法对含有吡啶、炔键和噻吩的两个系列的有机共轭化合物的结构、电离能、电子亲合势、吸收和发射光谱的性质及其机理以及一系列金属有机配合物的电子结构、吸收和发射光谱进行了研究。我们应用密度泛函(DFT)及单组态相互作用(CIS)方法对中性粒子的基态和激发态结构进行优化得知两个系列化合物都是平面结构，而且这种平面结构不随单元数量的增多而变化。我们分别以基态、激发态结构为基础，运用含时密度泛函(TD—DFT)方法研究了这些化合物的吸收和发射光谱，每一个化合物的最低能吸收带都具有π→π~*的跃迁性质，最低能荧光发射都具有冗π~*→π的跃迁性质。我们运用相同的方法结合极化连续模型研究了金属铱配合物在四氢呋哺溶液中的结构及其发光机制，我们发现最低能吸收都是从金属d轨道到配体π轨道的跃迁，最低能磷光发射都是具有配体π轨道到金属d轨道的跃迁。更多还原

【Abstract】 Structures, ionization potentials, electron affinities, absorption and emission properties of two families of π-conjugated oligomers and a series of Ir(III) complexes are studied by the quantum chemical methods. The ground and excited state geometry structures of the neutral molecules are optimized by DFT and CIS method. It is indicated that the structures are near planar and these planar geometries are hardly perturbed by the increasing of the unit number. Base on the structures of ground and excited states, we investigate the absorption and emission spectra using TD-DFT method. The lowest-lying absorption are assigned to π→π~* transition and the lowest-energy emission are attributed to π~*→π transition. Furthermore, the absorption and emission spectra of the iridium (Ⅲ) complexes in tetrahydrofuran (THF) solution are studied by TD-DFT method associated with PCM model. The results show that the lowest-lying absorption is described as MLCT, the lowest-energy phosphorescent emission is assigned to ~3MLCT更多还原