取代基团修饰苯基吡啶类铱磷光配合物的合成、结构及光物理性能  

Syntheses,structures,and photo⁃physical properties of iridium phosphorescent complexes with phenylpyridine derivatives bearing different substituting groups

作　　者：常桥稳[1,2] 张柯 黄光英 李诺楠 刘伟平[1] 白福全 晏彩先[1] 冯洋洋[1] 左川[1] CHANG Qiaowen;ZHANG Ke;HUANG Guangying;LI Nuonan;LIU Weiping;BAI Fuquan;YAN Caixian;FENG Yangyang;ZUO Chuan(State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals,Kunming Institute of Precious Metals,Yunnan Precious Metals Lab,Kunming 650106,China;Faculty of Material Science and Engineering,Kunming University of Science and Technology,Kunming 650093,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,稀贵金属综合利用新技术国家重点实验室,云南省贵金属实验室有限公司,贵研化学材料(云南)有限公司,昆明650106 [2]昆明理工大学材料科学与工程学院,昆明650093 [3]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》2025年第2期235-244,共10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);云南贵金属实验室科技计划项目(No.YPML-2022050230);云南省金属有机分子材料与器件重点实验室(No.202405AV340008)资助。

摘　　要：为研究取代基对铱磷光配合物光物理性质的影响,以2,4-二(2,4-二取代基苯基)吡啶[2,4-(2,4-2R-phenyl)2py,R=甲基(HL1)、甲氧基(HL2)、氟(HL3)、三氟甲基(HL4)]为主配体,即在主配体上2个苯基的2位和4位同时引入4个相同的甲基、甲氧基、氟或三氟甲基,同时以乙酰丙酮(Hacac)为辅助配体,合成出4个铱磷光配合物(Ln)2Ir(acac)[n=1(Ir1)、2(Ir2)、3(Ir3)、4(Ir4)]。通过元素分析、核磁共振谱(1H NMR和13C NMR)和单晶X射线衍射表征了铱磷光配合物的组成、空间结构和分子堆积。通过溶液和固态光致发光光谱、紫外可见吸收光谱、荧光寿命和理论计算对铱磷光配合物的光物理性能进行了深入和系统的研究。结果表明:4个铱磷光配合物均呈稍微扭曲的八面体构型,中心IrⅢ分别与2个主配体的C和N原子配位形成五元螯合环,同时和辅助配体acac-的2个氧原子配位形成稳定的六元螯合环。配合物Ir1、Ir2、Ir3和Ir4在溶液状态下的发射波长分别为537、515、514和553 nm,溶液中量子产率分别为68%、83%、88%和81%,荧光寿命分别为26.75、163.93、64.50和330.39 ns。4个铱磷光配合物具有不同的电子云分布特征,取代基能够调控电子云在苯环上的分布,进一步实现发射波长、发光颜色,荧光寿命和分子堆积的调控。To study the effect of substituents on the photo-physical properties of iridium phosphorescent complexes,four identical methyl(Me),methoxy(MeO),fluorine(F),or trifluoromethyl(CF3)groups were introduced into the 2-and 4-positions of the two phenyl groups onto the 2,4-bis(2,4-disubstituted phenyl)pyridine[2,4-(2,4-2R-phenyl)2py,R=Me(HL1),MeO(HL2),F(HL3),CF3(HL4)]main ligands at the same time.Four iridium phosphorescent complexes(Ln)2Ir(acac)[n=1(Ir1),2(Ir2),3(Ir3),4(Ir4)]were synthesized by using HL1,HL2,HL3,or HL4 as the main ligand and acetylacetone(Hacac)as the auxiliary ligand.The composition,spatial structure,and molecular stacking of all iridium phosphorescent complexes were characterized by elemental analysis,nuclear magnetic resonance spectroscopy(1H NMR and 13C NMR),and single-crystal X-ray diffraction.The results indicated that all four iridium phosphorescent complexes exhibit slightly distorted octahedral configurations.The central iridiumcoordinates with the C and N atoms of the two main ligands to form a five-membered chelating ring while coordinating with the two oxygen atoms of the acetylacetone auxiliary ligand to form a stable six-membered chelating ring.The results are consistent with the chemical structure of the target compound.A comprehensive and systematic study was conducted on the photophysical properties of iridium phosphorescent complexes through solution and solid photoluminescence spectroscopy,UV-Vis absorption spectroscopy,fluorescence lifetime,and theoretical calculations.The complexes Ir1,Ir2,Ir3,and Ir4 in solution with the photoluminescence quantum yields of 68%,83%,88%,and 81%exhibited maximum emission peaks at 537,515,514,and 553 nm,fluorescence lifetime of 26.75,163.93,64.50,and 330.39 ns,and in solid with maximum emission peaks at 536,520,520,and 546 nm,respectively.Four iridium phosphorescent complexes have different electron cloud distribution characteristics,and substituents can regulate the distribution of electron clouds on the benzene ring,further achieving the control of

关 键 词：铱(Ⅲ)配合物 磷光材料 取代基 苯基吡啶 光物理性能 

分 类 号：O614.825[理学—无机化学]