Li Yan, Zou Lu-Yi, Ren Ai-Min, Ma Ming-Shuo, Fan Jian-Xun
School of Chemical and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin University, Changchun Jilin (P.R. China), Fax: (+86) 431-88498567.; School of Chemical and Pharmaceutical Engineering, Jilin Institute of Chemical Technology, Jilin Jilin (P.R. China).
Chemistry. 2014 Apr 14;20(16):4671-80. doi: 10.1002/chem.201304660. Epub 2014 Mar 5.
The ground and excited states, charge injection/transport, and phosphorescence properties of eleven carbazole- and triphenylamine-functionalized Ir(III) complexes were investigated by using the DFT method. By analyzing the spin-orbit coupling (SOC) matrix elements, radiative decay rate constants k(r), and the electronic structures and energies at the S₀(opt) and T₁(opt) states, it was possible to rationalize the order of the experimental phosphorescence quantum yields of a series of Ir(III) complexes and to predict that [Ir(Nph-2-Cz-tz)3] has a higher phosphorescence quantum yield than [Ir(TPA-tz)3] (TPA=triphenylamine, tz=thiazolyl, Cz=carbazole, Nph=N-phenyl). Carbazole-functionalized Ir(III) complexes were shown to be efficient phosphorescent materials that have not only fast but also balanced electron/hole-transport performance as well as high phosphorescence quantum yields. The phosphorescence emission spectra can be modulated by modifying or replacing a pyridyl substituent.
采用密度泛函理论（DFT）方法研究了11种咔唑和三苯胺功能化的Ir(III)配合物的基态和激发态、电荷注入/传输及磷光性质。通过分析自旋轨道耦合（SOC）矩阵元、辐射衰减速率常数k(r)以及S₀(opt)和T₁(opt)态的电子结构和能量，能够合理地解释一系列Ir(III)配合物实验磷光量子产率的顺序，并预测[Ir(Nph-2-Cz-tz)3]比[Ir(TPA-tz)3]具有更高的磷光量子产率（TPA = 三苯胺，tz = 噻唑基，Cz = 咔唑，Nph = N-苯基）。咔唑功能化的Ir(III)配合物被证明是高效的磷光材料，不仅具有快速且平衡的电子/空穴传输性能，还具有高磷光量子产率。磷光发射光谱可通过修饰或取代吡啶基取代基来调节。
