苯并咪唑基Ir(Ⅲ)配合物的合成、结构和发光行为的调控或转换
Benzoimidazole-Based Cyclometalated Ir(Ⅲ) Complexes: Syntheses, Structures and Luminescence Modulation/Switching
作者单位E-mail
芮凯 南京大学化学化工学院, 南京 210093  
吴石山 南京大学化学化工学院, 南京 210093  
曹登科 南京大学化学化工学院, 南京 210093 dkcao@nju.edu.cn 
摘要: 合成了2个新的铱配合物[Ir(ppy)(qbiH)]NO31·NO3)和[Ir(ppy)(qbi)](2)。晶体结构分析表明,配合物1·NO32中的[Ir(ppy)2]+单元分别与苯并咪唑基的中性配体qbiH与阴离子配体qbi-螯合。在溶液以及在固态条件下,2个配合物表现出明显不同的发光行为。1·NO32在CH2Cl2溶液中的磷光发射波长分别为581和574 nm。在固态,1·NO3和2分别发红色(616 nm)与桔色(598 nm)的磷光。有趣的是,1·NO32在Et3N或TFA蒸汽的作用下,表现出红光发射与桔光发射之间的转换,这是因为它们的配体qbiH和qbi-发生了酸碱诱导的结构转换。此外,还讨论了配合物1·NO32的结构与发光行为之间的关系。
关键词: 铱配合物  晶体结构  光发射的转换或调控
基金项目: 国家自然科学基金(No.21871134)资助项目。
Abstract: Two iridium complexes[Ir(ppy)(qbiH)]NO3 (1·NO3) and[Ir(ppy)(qbi)] (2) have been synthesized. Their crystal structures indicate that an[Ir(ppy)2]+ unit is chelated by a neutral benzoimidazole-based ligand qbiH in 1·NO3, while anion ligand qbi- in 2. The different deprotonation degrees of ligands qbiH and qbi- in the two complexes lead to their clear differences in luminescence both in solution and in solid state. Complexes 1·NO3 and 2 in CH2Cl2 show the emissions at 581 and 574 nm, respectively. In solid state, a red emission at 611 nm was observed for 1·NO3, while an orange emission at 598 nm for 2. It is interesting that both 1·NO3 and 2 in solid state exhibited luminescence switching between red emission and orange emission, upon meeting Et3N/TFA vapor. This is due to the acid/base-induced structural interconversion between ligand qbiH and ligand qbi- in complexes 1·NO3 and 2. Moreover, we discuss the relationship between structure and luminescence for 1·NO3 and 2.
Keywords: iridium complex  crystal structure  luminescence modulation/switching
投稿时间:2019-04-04 修订日期:2019-04-26
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芮凯,吴石山,曹登科.苯并咪唑基Ir(Ⅲ)配合物的合成、结构和发光行为的调控或转换[J].无机化学学报,2019,35(8):1340-1348.
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