取代基位置对2,4-二苯基吡啶类铱磷光配合物光物理性能的影响  

The Effect of Substituent Position on Photophysical Properties of Iridium Phosphorescent Complexes Based on Substituted 2,4-Diphenylpyridine

作　　者：常桥稳[1] 陈祝安 晏彩先[1] 刘伟平[1] 冯洋洋[1] CHANG Qiao-wen;CHEN Zhu-an;YAN Cai-xian;LIU Wei-ping;FENG Yang-yang(State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals,Yunnan Precious Metals Lab Co.,Ltd.,Kunming Institute of Precious Metals,Kunming 650106,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,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,云南昆明650106

出　　处：《光谱学与光谱分析》2024年第2期504-509,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21861023);中央引导地方自由探索类项目(202207AA110006);云南省重点基金项目(2019FA047);云南省院所技术开发专项(202004AR040001);云南省金属有机分子材料与器件重点实验室项目(202205AD160053);云南省贵金属实验室科技计划项目(YPML-2022050230)资助。

摘　　要：铱磷光配合物具有高的发光效率、良好的热稳定性和发光颜色容易调节等优势,在有机发光二极管(OLED)、电化学发光池(LEC)、光催化、肿瘤诊断和传感器等领域有着重要的应用前景,是综合性能最优的电致磷光配合物。其颜色调控主要通过改变主配体和辅助配体的化学结构来实现,如通过改变配体的共轭程度、在配体上引入具有不同供/吸电子能力的取代基、在不同位置引入相同的取代基等方式可以实现发光颜色的调节,其中取代基的位置对铱磷光配合物光物理性能影响的研究较少。研究甲基处于不同取代位置对铱磷光配合物光物理性能的影响,以甲基处于2位和4位或3位和5位的2,4-二苯基吡啶为主配体、2,2,6,6-四甲基庚二酮为辅助配体,合成出2个新的铱磷光配合物(2,4-2Me-dppy)_(2)Ir(tmd)和(3,5-2Me-dppy)_(2)Ir(tmd)。通过元素分析、核磁共振谱和单晶X射线衍射等测试了配合物的组成和空间结构,两个配合物均呈稍微扭曲的八面体构型,空间群分别为C 12/c 1和P-1,晶系分别为单斜和三斜;通过热重分析研究了配合物的热稳定性,两个配合物均具有较好的热稳定性,热分解温度分别为307和318℃;通过紫外可见光谱和光致发光光谱研究了配合物的光物理性能,两个配合物在溶液中发射波长分别为545和572 nm,溶液中量子产率分别为70%和92%。进一步探讨了取代基位置对铱磷光配合物光物理性能的影响,研究发现:甲基所处的位置对2,4-二苯基吡啶类铱磷光配合物的发光颜色和发射波长有着显著的影响。与甲基处于2位和4位得到的铱磷光配合物相比,甲基处于3位和5位时得到的铱配合物的发射波长产生了明显的红移,为纯正的黄光发射,是一种潜在的黄光材料,并有望在OLED照明中得到应用。Phosphorescent iridium complexes are the electroluminescent materials with the best comprehensive performance.Phosphorescent iridium complexes have been employed in organic light-emitting diodes(OLEDs),electrochemical light-emitting cells(LECs),photocatalysis,tumour diagnosis and sensors owing to their various advantages such as high quantum efficiency,good thermal stability and tunable emission colors.The color tuning of the iridium phosphorescent complex can be realized by changing the chemical structure of the main ligands and auxiliary ligands such as changing the conjugation degree of ligand,electron-donating and with drawing ability of substituents and substituent position.The influence of substituent position on iridium phosphorescent complex's photophysical properties was rarely researched.In this paper,we propose studying the effect of different substitution positions of methyl groups on the photophysical properties of iridium phosphorescent complexes.Two new iridium phosphorescence complexes(2,4-2Me-2,4-dppy)_(2)Ir(tmd)and(3,5-2Me-dppy)_(2)Ir(tmd)were synthesized with 2,4-diphenylpyridine of different methyl substituent positions as the main ligand and 2,2,6,6-tetramethylheptanedione as the auxiliary ligands.Their composition and spatial structure were characterized by elemental analysis,nuclear magnetic resonance(1H NMR and 13C NMR)and single-crystal X-ray diffraction.Bothcomplexes show slightly distorted octahedral configuration with space groups of C 12/C 1 and P-1,with monoclinic and triclinic crystal systems,respectively.The thermal stability was tested by TG curves,the two complexes have good thermal stability with thermal decomposition temperatures of 307℃and 318℃respectively.UV-Vis spectra and photoluminescence spectra studied the photophysical properties of the complexes.The emission wavelengths of the two complexes in solution were 545 and 572 nm,respectively.The quantum yields in solution were 70%and 92%,respectively.The effect of substituent position on the photophysical properties of ir

关 键 词：铱配合物 磷光材料 苯基吡啶 取代基位置 光物理性能 影响 

分 类 号：TF803.21[冶金工程—有色金属冶金]