辅助配体联吡啶环上的取代基对铱配合物光物理性能的影响  

Effects of substituents on the bipyridine ring of the auxiliary ligand on photophysical properties of iridium complexes

作　　者：晏彩先 黄光英 张柯 陈祝安 常桥稳 侯文明 YAN Caixian;HUANG Guangying;ZHANG Ke;CHEN Zhu’an;CHANG Qiaowen;HOU Wenming(State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals,Yunnan Precious Metals Lab Co.Ltd.,Kunming 650106,China)

机构地区：[1]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

出　　处：《贵金属》2024年第3期21-27,共7页Precious Metals

基　　金：云南贵金属实验室科技计划项目(YPML-2023050217、YPML-2023050235);云南省技术创新人才培养项目(202205AD160053);云南省金属有机分子材料与器件重点实验室(202205AG070004)。

摘　　要：以1-(3,5-二甲基苯基)异喹啉(mpiq)为环金属主配体,再分别以4,4'-二叔丁基-2,2'-联吡啶(dtbbpy)和4,4'-二溴-2,2'-联吡啶(dibbpy)为辅助配体,设计合成出两种新型阳离子型铱配合物[Ir(mpiq)_(2)(dtbbpy)]PF_(6)(R1)和[Ir(mpiq)_(2)(dibbpy)]PF_(6)(R2)。通过质谱、元素分析、红外光谱、核磁共振谱(^(1)H和^(13)C)和X射线单晶衍射等表征手段,确定了它们的组成和化学结构,通过紫外可见光谱和光致发光光谱研究了它们的光物理性能,并同时测试了它们的热稳定性。测试结果表明,配合物R1和R2都具有较好的热稳定性,其最大发射波长依次为598 nm和613 nm,发光颜色由黄色-红色变化。在辅助配体中引入给电子基团-C(CH_(3))_(3),配合物电子云发生聚集,而引入吸电子基团-Br,配合物的电子云分散。两个配合物相比,R1发生蓝移,R2发生红移。Two new ionic iridium(III)complexes,[Ir(mpiq)_(2)(dtbbpy)]PF_(6)(R1)and[Ir(mpiq)_(2)(dibbpy)]PF_(6)(R2),were synthesized by choosing 1-(3,5-dimethylphenyl)isoquinoline(mpiq)as the cyclometalated ligand and 4,4'-di-tert-butyl-2,2'-bipyridine(dtbpy)and 4,4'-dibromo-2,2'-bipyridine(dibbpy)as the auxiliary ligand of R1 and R2,respectively.The compositions and chemical structures of the complexes were characterized by elemental analysis,mass spectrometry,nuclear magnetic resonance spectroscopy and infrared spectroscopy along with single-crystal X-ray diffraction,and the photophysical properties were measured by using UV-visible and photoluminescence spectroscopy.The thermal stability was tested by thermogravimetric analysis.The results show that the complexes R1 and R2 have good thermal stability.Their maximum emission wavelengths are 598 nm and 613 nm,and the cooresponding emitting color is yellow and red-greenish,respectively.The substituent group in the auxiliary ligand has some effect on the mission wavelengths of the complexes.When the electron-donating group-C(CH_(3))_(3) is introduced,the electron cloud of the complex molecules will be aggregated,leading to a decrease in the mission wavelength.On the contrary,the electron-drawing group Br introduced in the auxiliary ligand disperses the electron cloud of the molecules,as a result,the mission wavelength will be red-shifted.

关 键 词：金属有机光化学 阳离子型铱配合物 异喹啉类 发光电化学池 光物理性能 

分 类 号：O627.8[理学—有机化学]