Di Censo Davide, Fantacci Simona, De Angelis Filippo, Klein Cedric, Evans Nick, Kalyanasundaram K, Bolink Henk J, Grätzel Michael, Nazeeruddin Mohammad K
Laboratory for Photonics and Interfaces, Station 6, Institute of Chemical Sciences and Engineering, School of basic Sciences, Swiss Federal Institute of Technology, CH-1015 Lausanne, Switzerland.
Inorg Chem. 2008 Feb 4;47(3):980-9. doi: 10.1021/ic701814h. Epub 2008 Jan 3.
Highly phosphorescent blue-light-emitting anionic iridium complexes (C4H9)4N[Ir(2-phenylpyridine)2(CN)2] (1), (C4H9)4N[Ir(2-phenyl-4-dimethylaminopyridine)2(CN)2] (2), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-pyridine)2(CN)2] (3), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (4), and (C4H9)4N[Ir(2-(3,5-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (5) were synthesized and characterized using NMR, UV-vis absorption, and emission spectroscopy and electrochemical methods. In these complexes color and quantum yield tuning aspects are demonstrated by modulating the ligands with substituting donor and acceptor groups on both the pyridine and phenyl moieties of 2-phenylpyridine. Complexes 1-5 display intense photoluminescence maxima in the blue region of the visible spectrum and exhibit very high phosphorescence quantum yields, in the range of 50-80%, with excited-state lifetimes of 1-4 micros in acetonitrile solution at 298 K. DFT and time dependent-DFT calculations were performed on the ground and excited states of the investigated complexes to provide insight into the structural, electronic, and optical properties of these systems.
合成了高磷光性的蓝色发光阴离子铱配合物（C4H9）4N[Ir(2 - 苯基吡啶)2(CN)2]（1）、（C4H9）4N[Ir(2 - 苯基 - 4 - 二甲基氨基吡啶)2(CN)2]（2）、（C4H9）4N[Ir(2 - (2,4 - 二氟苯基) - 吡啶)2(CN)2]（3）、（C4H9）4N[Ir(2 - (2,4 - 二氟苯基) - 4 - 二甲基氨基吡啶)2(CN)2]（4）和（C4H9）4N[Ir(2 - (3,5 - 二氟苯基) - 4 - 二甲基氨基吡啶)2(CN)2]（5），并使用核磁共振、紫外 - 可见吸收、发射光谱和电化学方法对其进行了表征。在这些配合物中，通过在2 - 苯基吡啶的吡啶和苯基部分上用供体和受体取代基团调节配体，展示了颜色和量子产率的调节方面。配合物1 - 5在可见光谱的蓝色区域显示出强烈的光致发光最大值，并表现出非常高的磷光量子产率，在50 - 80%的范围内，在298 K的乙腈溶液中的激发态寿命为1 - 4微秒。对所研究配合物的基态和激发态进行了密度泛函理论（DFT）和含时密度泛函理论（TD - DFT）计算，以深入了解这些体系的结构、电子和光学性质。
