两种联吡啶钌配合物的合成及性能  

Synthesis and properties of two bipyridine ruthenium complexes

作　　者：张柯 黄光英 陈祝安 晏彩先[1] 常桥稳[1] 冯洋洋 ZHANG Ke;HUANG Guangying;CHEN Zhu’an;YAN Caixian;CHANG Qiaowen;FENG Yangyang(Yunnan Precious Metals Laboratory Co.,Ltd.,Kunming Institute of Precious Metals,State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals,Kunming 650106,China;Guiyan Chemical Materials(Yunnan)Co.Ltd.,Kunming 650106,China)

机构地区：[1]云南贵金属实验室有限公司,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,昆明650106 [2]贵研化学材料(云南)有限公司,昆明650503

出　　处：《贵金属》2024年第S01期182-187,共6页Precious Metals

基　　金：云南贵金属实验室科技计划项目(No.YPML-2022050230);中央引导地方自由探索项目(No.202207AA110006);云南省金属有机分子材料与器件重点实验室项目(No.202205AD160053);云南贵金属实验室科技计划项目(No.YPML-2023050217)。

摘　　要：钌配合物凭借其独特的光物理和光化学特性,在光氧化还原催化、细胞成像、有机发光二极管(OLEDs)和染料敏化太阳能电池(DSSCs)等重要领域表现出广泛的应用前景。目前,关于5,5'-二(三氟甲基)-2,2'-联吡啶(CF_(3)-bpy)配体的异质钌配合物研究较少。本文以2,2-联吡啶和5,5-三氟甲基取代的联吡啶为第一配体,以壬烷取代联吡啶为第二配体,成功合成出两种异质钌配合物。通过核磁共振氢谱和红外光谱表征了配合物的结构,通过紫外可见光谱、光致发光光谱和循环伏安曲线研究了配合物的光物理和电化学性质,探索了三氟甲基取代对配合物光物理性能的影响。结果表明,三氟甲基的引入使钌配合物在450 nm附近出现额外不同的吸收带,对应于不同配体与钌金属中心间的电荷转移的MLCT态。同时,配合物的光致发光强度明显降低,最大发射波长红移了50 nm,表明三氟甲基修饰使配合物^(3)MLCT态能显著改变,对配合物发光性能有重要影响。两种配合物具有相似的电化学性质,但引入三氟甲基会使钌配合物的氧化电位更正。Ruthenium complexes exhibit a wide range of applications in important fields such as photoredox catalysis,cellular imaging,organic light-emitting diodes(OLEDs)and dye-sensitised solar cells(DSSCs)due to their unique photophysical and photochemical properties.Currently,heterogeneous ruthenium complexes of 5,5‘-bis(trifluoromethyl)-2,2’-bipyridine(CF_(3)-bpy)ligands are less studied.In this paper,two heterogeneous ruthenium complexes were successfully synthesised using 2,2-bipyridine and 5,5-trifluoromethyl-substituted bipyridine as the first ligand and nonane-substituted bipyridine as the second ligand.The structures of the complexes were characterised by nuclear magnetic resonance(NMR)hydrogen spectroscopy and infrared spectroscopy,and the photophysical and electrochemical properties of the complexes were investigated by UV-visible spectroscopy,photoluminescence spectroscopy and cyclic voltammetry curves,and the effect of trifluoromethyl substitution on the photophysical properties of the complexes was explored.The results showed that the introduction of trifluoromethyl group caused the ruthenium complexes to show additional different absorption bands near 450 nm,which correspond to the MLCT states of charge transfer between different ligands and ruthenium metal centres.Meanwhile,the photoluminescence intensity of the complex was significantly reduced and the maximum emission wavelength was red-shifted by 50 nm,indicating that the trifluoromethyl modification caused a significant change in the ^(3)MLCT,which had an important effect on the luminescence performance of the complex.The two complexes have similar electrochemical properties,but the introduction of trifluoromethyl causes the oxidation potential of the ruthenium complex to be more positive.

关 键 词：钌配合物 三氟甲基 合成 光物理性能 电化学性质 

分 类 号：O614.821[理学—无机化学]