Authentic-Blue Phosphorescent Iridium(III) Complexes Bearing Both Hydride and Benzyl Diphenylphosphine; Control of the Emission Efficiency by Ligand Coordination Geometry

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• 作者：Yuan-Chieh Chiu ; Chen-Huey Lin ; Jui-Yi Hung ; Yun Chi ; Yi-Ming Cheng ; Kang-Wei Wang ; Min-Wen Chung ; Gene-Hsiang Lee ; Pi-Tai Chou
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：September 7, 2009
• 年：2009
• 卷：48
• 期：17
• 页码：8164-8172
• 全文大小：908K
• 年卷期：v.48,no.17(September 7, 2009)
• ISSN：1520-510X

文摘

Sequential treatment of IrCl₃·nH₂O with 2 equiv of benzyl diphenylphosphine (bdpH) and then 1 equiv of 3-trifluoromethyl-5-(2-pyridyl) pyrazole (fppzH) in 2-methoxyethanol gave formation to three isomeric complexes with formula [Ir(bdp)(fppz)(bdpH)H] (1−3). Their molecular structures were established by single crystal X-ray diffraction studies, showing existence of one monodentate phosphine bdpH, one terminal hydride, a cyclometalated bdp chelate, and a fppz chelate. Variation of the metal−ligand bond distances showed good agreement with those predicted by the trans effect. Raman spectroscopic analyses and the corresponding photophysical data are also recorded and compared. Among all isomers complex 1 showed the worst emission efficiency, while complexes 2 and 3 exhibited the greatest luminescent efficiency in solid state and in degassed CH₂Cl₂ solution at room temperature, respectively. This structural relationship could be due to the simultaneously weakened hydride and the monodentate bdpH bonding that are destabilized by the trans-pyrazolate anion and cyclometalated benzyl group, respectively.