Abstract

采用密度泛函的B3LYP和UB3LYP方法分别优化了一系列[Ru(iph)(L)2]2+(L=cpy(1),mpy(2),npy(3);其中iph为2,9-双(1′-甲基-2′-咪唑)-1,10-邻二氮杂菲,cpy为4-氰基嘧啶,mpy为4-甲基嘧啶,npy为4-氮二甲基嘧啶)配合物的基态和激发态结构.利用含时密度泛函理论(TD-DFT)方法,结合极化连续介质(PCM)模型计算了它们在丙酮溶液中的吸收和发射光谱.研究结果表明:优化得到的几何结构参数和相应的实验值符合得非常好.1和2的最高占据分子轨道主要由金属的d轨道和iph配体的π轨道构成,但是3主要占据在npy配体上,而它们的最低空轨道主要由iph配体的π反键轨道占据.因此,1和2的最低能吸收和发射属于金属到配体(MLCT)和配体内部(ILCT)的电荷转移跃迁,而3属于两个配体之间的电荷转移(LLCT)跃迁.三个配合物的最低能吸收分别在509nm(1),527nm(2)和563nm(3),其磷光发射分别在683nm(1),852nm(2)和757nm(3).这显示出通过调节L配体的π电子给予能力可以改变最低能吸收和发射的跃迁性质和发光颜色.

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