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：常桥稳[1] 陈祝安 冯璐 姜雯 晏彩先[1] 刘伟平[1] 白福全 CHANG Qiao-Wen;CHEN Zhu-An;FENG Lu;JIANG Wen;YAN Cai-Xian;LIU Wei-Ping;BAI Fu-Quan(State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals,Kunming Institute of Precious Metals,Kunming Guiyan New Material Technology Co.,Ltd.,Yunnan Precious Metals Lab Co.,Ltd.,Kunming 650106,China;Institute of Theoretical Chemistry,College of Chemistry,Jilin University,Changchun 130023,China)

机构地区：[1]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 [2]吉林大学化学学院,理论化学研究所,长春130023

出　　处：《无机化学学报》2023年第2期255-262,共8页Chinese Journal of Inorganic Chemistry

基　　金：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);云南省金属有机分子材料与器件重点实验室(No.202205AD160053)资助。

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(CF_(3)),合成出3个铱磷光配合物(2,4-2R-mpq)_(2)Ir(tmd)(R=F(1)、MeO(2)、CF_(3)(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CF_(3),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。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)_(2)Ir(tmd)(R=F(1),MeO(2),CF_(3)(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 Me O 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 CF_(3)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.CCDC:2217725,1;2217726,2;2217727,3.

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 

分 类 号：O614.825[理学—无机化学]