含不同取代吲哚修饰的方酸菁衍生物的合成及光学性能的研究  

Synthesis and Optical Properties of Different Substituted-Indole-Modified Squaraine Derivatives

作　　者：张碧玮 袁展翔 徐建兴 籍少敏[1] 霍延平[1] 梁亮[1] Zhang Biwei;Yuan Zhanxiang;Xu Jianxing;Ji Shaomin;Huo Yanping;Liang Liang(School of Chemicals Engineering and Light Industry,Guangdong University of Technology,Guangzhou 510006)

机构地区：[1]广东工业大学轻工化工学院,广州510006

出　　处：《有机化学》2020年第9期2929-2937,共9页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21975053,21975055)资助项目。

摘　　要：通过缩合反应合成了四个含不同取代吲哚修饰的方酸菁衍生物(SQ、DISQ、MeSQ、DIMeSQ).方酸菁衍生物是一种D-A-D构型的染料,由方酸与两个富电子基团通过共轭连接而成.化合物结构通过1H NMR,13C NMR和高分辨质谱进行表征.同时,对于它们的紫外-可见吸收、荧光发射、荧光量子产率、荧光寿命及单线态氧量子产率等光物理性质也做了研究.结果显示,在二氯甲烷溶液中,SQ、DISQ、MeSQ和DIMeSQ的吸收波长在600~700 nm,发射波在620~800 nm,均在近红外区域.在应用方面,4个方酸菁衍生物敏化单线态氧性能被研究,其中DISQ获得最高的单线态氧量子产率(6%),是DIMeSQ的2倍(3%),可能因为N-氢取代分子相比N-甲基取代分子,更有利于分子的系间窜跃.结合单晶结构和理论计算证明分子内N—H…O作用力有利于分子的系间窜跃,表明分子DISQ可以作为光动力治疗的潜在药物.Four squaraine derivatives SQ,DISQ,MeSQ and DIMeSQ with different substitution indole modifications were synthesized through condensation reaction.Squaraine derivative is one kind of D-A-D configuration dyes,which is formed by connecting squaraine with two electron-rich groups through conjugation.The squaraine derivatives were characterized by 1 H NMR,13 C NMR and high resolution mass spectrometry.The photophysical properties of these squaraine derivatives were studied,such as UV-visible absorption,fluorescence emission,fluorescence quantum yield,fluorescence lifetimes,singlet oxygen quantum yields,and so on.The results showed that,SQ,DISQ,MeSQ and DIMeSQ showed stronger absorption band at 600~700 nm and emission band at 620~800 nm in dichloromethane,which were in near-infrared filed.These four squaraine derivatives were used for singlet oxygen generation,and the highest singlet oxygen quantum yield(6%)was observed for DISQ,which is twice as high as that of DIMeSQ(3%).It is proposed that iodine-substituted and N-hydrogensubstituted molecules are more conducive to intersystem crossing than N-methyl substituted molecules.In addition,It is confirmed that the intramolecular N—H…O force is beneficial to the intersystem crossing of molecules by combining single crystal structure and theoretical calculations.It showed that DISQ could be used as a potential drug for photodynamic therapy.

关 键 词：方酸菁衍生物 三重态 单线态氧 系间窜跃 

分 类 号：TQ460.1[化学工程—制药化工]