吸电子基团调控苯基喹啉类铱配合物的合成及光物理性能 |
Synthesis and photophysical properties of phenylquinoline iridium complexes controlled by electron-withdrawing groups |
作者 | 单位 | E-mail | 常桥稳 | 昆明贵金属研究所, 昆明贵研新材料科技有限公司, 稀贵金属综合利用新技术国家重点实验室, 云南贵金属实验室有限公司, 昆明 650106 | | 陈祝安 | 昆明贵金属研究所, 昆明贵研新材料科技有限公司, 稀贵金属综合利用新技术国家重点实验室, 云南贵金属实验室有限公司, 昆明 650106 | | 冯璐 | 吉林大学化学学院, 理论化学研究所, 长春 130023 | | 姜雯 | 昆明贵金属研究所, 昆明贵研新材料科技有限公司, 稀贵金属综合利用新技术国家重点实验室, 云南贵金属实验室有限公司, 昆明 650106 | | 晏彩先 | 昆明贵金属研究所, 昆明贵研新材料科技有限公司, 稀贵金属综合利用新技术国家重点实验室, 云南贵金属实验室有限公司, 昆明 650106 | ycx19860706@163.com | 刘伟平 | 昆明贵金属研究所, 昆明贵研新材料科技有限公司, 稀贵金属综合利用新技术国家重点实验室, 云南贵金属实验室有限公司, 昆明 650106 | | 白福全 | 吉林大学化学学院, 理论化学研究所, 长春 130023 | Baifq@jlu.edu.cn |
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摘要: 以2,2,6,6-四甲基庚二酮(tmd)为辅助配体,2,4-二取代基苯基-4-甲基喹啉(2,4-2R-mpq)为主配体,在主配体中苯基的2位和4位同时引入氟(F)、甲氧基(MeO)或三氟甲基(CF3),合成出3个铱磷光配合物(2,4-2R-mpq)2Ir(tmd)(R=F (1)、MeO (2)、CF3 (3))。通过元素分析、核磁共振谱和单晶X射线衍射表征了配合物的组成和分子结构。通过紫外可见吸收光谱、光致发光光谱和理论计算对配合物的光物理性能进行了研究。结果表明:3个配合物的晶体均为三斜晶系,空间群均为P1,呈稍微扭曲的八面体构型。配合物1、2和3在溶液状态下的发射波长分别为570、582和604 nm,溶液中量子产率分别为96%、80%和80%。在主配体中苯基的2位和4位同时引入F或MeO,配合物电子云发生聚集,而引入CF3,配合物的电子云分散。与配合物3相比,配合物1和2的发射波长发生了显著的蓝移 |
关键词: 铱(Ⅲ)配合物 磷光材料 苯基喹啉 吸电子基团 光物理性能 |
基金项目: 国家自然科学基金(No.21861023)、中央引导地方自由探索项目(No.202207AA110006)、云南省自然科学基金重点项目(No.2019FA047)、云南贵金属实验室科技计划项目(No.YPML-2022050230)、云南省创新引导与科技型企业培育计划(No.202004AR040001)和云南省金属有机分子材料与器件重点实验室(No.202205AD160053)资助 |
Abstract: To study the effect of substituents on iridium phosphorescent complexes, fluorine, methoxy, or trifluoromethyl were introduced into positions 2 and 4 of phenyl at the same time to obtain 2, 4-disubstituted phenyl-4-methylquinoline (2, 4-2R-mpq). Three new iridium phosphorescent complexes (2, 4-2R-mpq)2Ir(tmd) (R=F (1), MeO (2), CF3 (3)) were synthesized by using 2, 2, 6, 6-tetramethylheptanedione (tmd) as the auxiliary ligand, and 2, 4-2R-mpq with the electron-withdrawing group as the main ligands. The compositions and chemical structures of the complexes were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction. The three iridium complexes belong to the triclinic system with the P1 space group. The photophysical properties of the complexes were studied by UV-Vis absorption spectroscopy, photoluminescence spectroscopy, and theory calculation. The results indicate that complexes 1, 2, and 3 with the photoluminescence quantum yields of 96%, 80%, and 80% exhibited maximum emission peaks at 570, 582, and 604 nm, respectively. When F and MeO are introduced into the 2 and 4 positions of phenyl on the main ligand, the electron cloud of complexes 1 and 2 are aggregated, while the CF3 is introduced, and the electron cloud of the complex is dispersed. Compared with complex 3, the emission wavelengths of complexes 1 and 2 had a significant blue shift. Different from traditional cognition, the methoxyl group represents an electron-withdrawing group. |
Keywords: iridium(Ⅲ) complexes phosphorescent materials phenylquinoline electron-withdrawing group photophysical properties |
投稿时间:2022-07-14 修订日期:2022-11-15 |
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常桥稳,陈祝安,冯璐,姜雯,晏彩先,刘伟平,白福全.吸电子基团调控苯基喹啉类铱配合物的合成及光物理性能[J].无机化学学报,2023,39(2):255-262. |
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