卤代苯溶剂对镓咔咯配合物光物理性质的影响外重原子效应.pdfVIP

March 物理化学学报(Wuli Huaxue Xueba01 Acta Phys．一Chim。Sin。2016，32(3)，77 1—779 771 [Article] doi：10．3866／PKU．WHXB201601043 www．whxb．pku．edu．cn 卤代苯溶剂对镓咔咯配合物光物理性质的影响：外重原子效应 占 轩1 赵 芳2 张 蕾2，‘ 吕标彪3 彭素红1 应 晓3 王 惠2·+ 刘海洋L2’+ (1华南理ST_大学化学系，广州510641；2中山大学光电材料与技术国家重点实验室，广州510275； 3华南理工大学应用物理系，广州510641) 摘要：利用紫外．可见光谱、稳态和时间分辨荧光光谱以及飞秒瞬态吸收光谱探测了不同卤代苯溶剂对三种 五氟苯基取代的镓咔咯(1-Ga、2-Ga、3-Ga)光物理性质的影响，结果表明卤代苯溶剂的色散力对于镓咔咯 电子光谱吸收峰位置的影响起着主要作用；溶剂外重原子效应能显著降低镓咔咯的荧光量子产率。飞秒瞬态 吸收光谱表明，光激发下，镓咔咯与卤代苯溶剂之间可发生电子转移反应，溶剂的重原子效应可以减缓电荷 分离态复合物电荷重组速率。 关键词：咔咯；镓：卤代苯溶剂；重原子效应；光物理性质 中图分类号：0641．06 Influence of Halogenated Benzene Solvents on the PhOtOphySicaI Properties of Gallium Corroles：the External Heavy Atom Effect ZHAN Xuanl ZHAO Fan92 ZHANG Lei2’L0 Biao—Bia03 PENG Su-Hon91 YING Xia03 WANG Hui2’LIU Hai-Yan91·2·’ (1Department ofChemistry,South China University ofTechnology,Guangzhou 510641，尸R．China； 2State Key Laboratory ofOptoelectronics Materials and Technologies，SunrYat Sen University,Guangzhou 510275，P R．China； 3Department ofApplied Pbsics，South China University oyTechnology,Guangzhou 510641．p R．China、 Abstract：The photophysical properties of pentafluorophenyl·substituted gallium corroles in halogenated benzenes were investigated using ultraviolet-visible(UV-Vis)，steady．state，time．resolved fluorescence，and femtosecond transient absorption spectroscopies．The results showed that the absorption maximum wavelength of the gallium corroles was mainly related to the dispersion force of the halogenated benzene solvents．The externaI heavy atom effect of halogenated benzenes may markedly Iower the fluorescence quantum yield of gallium corrole complexes．Photoinduced electron transfer between the gallium corroles and halogenated benzene solvents was detected by femtosecond transient absorption spectroscopy．The expedmental evidence showed that the heavy atom effect of the solvent might Iower the charge recombination rate of charge-sepa阳ted gallium corrole—solvent complexes． Key Words：Corrole；Gallium；Halogenated benzene solvent；Exter