新型吡啶甲酸类铱磷光材料的合成、晶体结构及性能  

Synthesis,Crystal Structure and Properties of Novel Pyridine Carboxylic Acid-based Iridium Phosphorescent Materials

作　　者：陈祝安 张柯 黄光英 晏彩先[1] 钱昱霏 常桥稳[1] CHEN Zhu’an;ZHANG Ke;HUANG Guangying;YAN Caixian;QIAN Yufei;CHANG Qiaowen(State Key Laboratory of New Technologies for Comprehensive Utilization of Rare and Precious Metals,Yunnan Laboratory of Precious Metals Co.,Ltd.,Kunming Institute of Precious Metals,Kunming 650106,China;Kunming First People s Hospital,Kunming 650000,China)

机构地区：[1]昆明贵金属研究所,云南贵金属实验室有限公司,稀贵金属综合利用新技术国家重点实验室,昆明650106 [2]昆明市第一人民医院,昆明650000

出　　处：《材料导报》2024年第S01期516-521,共6页Materials Reports

基　　金：中央引导地方自由探索类项目(202207AA110006);云南贵金属实验室科技计划项目(YPML-2022050230);云南省金属有机分子材料与器件重点实验室(202205AD160053)。

摘　　要：铱磷光材料由于发光效率高、热稳定性好、发光颜色易调控等优点,成为目前综合性能最优异的有机电致发光材料。Ir(C^N)2(L^X)型铱磷光配合物是最为重要的一类铱磷光发光材料,通过调控配体的化学结构,如引入供/吸电子基团、增大共轭程度等来达到改变发光颜色、发射波长和性能等目的。本工作从辅助配体着手,选用N^O型的吡啶甲酸衍生物为辅助配体,通过不同性质的基团对其结构进行调控;分别以3-三氟甲基-2-吡啶甲酸(Tricid)和异喹啉-1-甲酸(Qicid)为辅助配体,以2-(2,4-二氟苯基)-5-甲基吡啶(Medfppy)为主配体,设计合成出两种吡啶甲酸类铱磷光材料Ir1和Ir2。通过核磁共振谱、质谱和单晶X射线衍射等测试手段表征了它们的组成和化学结构,并确定了Ir1和Ir2的晶体结构,Ir1为单斜晶系,P2_(1)/c空间群;Ir2为三斜晶系,P-1空间群,均呈现出稍微扭曲的八面体构型;通过热重分析测试了材料的热稳定性,Ir1和Ir2的热分解温度分别为319℃和364℃;通过紫外-可见光谱和光致发光光谱研究了材料的光物理性能,Ir1和Ir2在二氯甲烷溶液中的最大发射波长分别为582 nm和607 nm;通过循环伏安法测试了材料的电化学性质,并计算得到材料的HOMO-LUMO能级。研究结果表明:与吡啶甲酸(Pic)上引入吸电子基团(-CF_(3))相比,增大共轭程度对铱磷光材料的发射波长作用程度较大;增大共轭程度不仅使配合物的最大发射波长产生了红移,还提高了材料的热稳定性,对设计新型的铱磷光材料具有一定的借鉴意义。Iridium phosphorescent materials have become the most excellent organic electroluminescent materials due to their high luminescence efficiency,good thermal stability,easy to regulate the color of luminescence,etc.Ir(C^N)2(L^X)-type iridium phosphorescent compounds are the most important class of iridium phosphorescent materials,which can change the color,emission wavelength and performance of luminescence through the modulation of ligands,such as the introduction of electron-donor/electro-absorbing groups and the increase of the degree of conjugation,etc.The luminescence of iridium phosphorescent materials is also a key factor in the development and production of iridium phosphorescent materials.By modulating the chemical structure of the ligand,such as introducing electron donor/absorber groups and increasing the degree of conjugation,we can change the luminescence color,emission wavelength and performance.In this work,N^O-type pyridine carboxylic acid derivatives were selected as auxiliary ligands,and different groups were used to regulate their structures.3-trifluoromethyl-2-pyridinecarboxylic acid(tricid)and isoquinoline-1-carboxylic acid(qicid)were used as auxiliary ligands,and 2-(2,4-difluorophenyl)-5-methylpyridine(medfppy)as the main ligand,respectively.Two pyridine carboxylic acid iridium phosphorescent materials,Ir1 and Ir2,were designed and synthesized,and their compositions and chemical structures were characterized by nuclear magnetic resonance(NMR)spectroscopy,mass spectrometry(MS),and single-crystal X-ray diffraction(XRD),and the crystal structures of Ir1 and Ir2 were determined,with Ir1 in monoclinic crystal system and P21/c space group and Ir2 in triclinic crystal system and P-1 space group,which both showed slightly twisted octahedral configurations;the materials were tested by thermogravimetric analysis.The thermal stability of the materials was tested by thermogravimetric analysis,and the thermal decomposition temperatures of Ir1 and Ir2 were 319℃and 364℃,respectively;the photophysical pro

关 键 词：铱磷光材料 辅助配体 吡啶甲酸衍生物 结构修饰 光物理性能 

分 类 号：O641.4[理学—物理化学] TB34[理学—化学]