柔性链连接的双-三苯胺类小分子和电化学聚合物的合成及其发光和电化学性能  

Synthesis, Luminescence and Electrochemical Properties of Bis-Triphenylamine-Based Small Molecules and Electrochemical Polymers Connected by Flexible Chains

作　　者：史宏宇 谈东兴 韩福社[1,2] SHI Hong-Yu;TAN Dong-Xing;HAN Fu-She(The Laboratory of Green Chemistry and Process,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026,China)

机构地区：[1]中国科学院长春应用化学研究所,绿色化学与过程实验室,长春130022 [2]中国科学技术大学应用化学与工程学院,合肥230026

出　　处：《应用化学》2025年第3期353-364,共12页Chinese Journal of Applied Chemistry

摘　　要：设计合成了3个由柔性酰胺或酯链连接的双-三苯胺类有机小分子1-3,通过电化学聚合(Electrochemical polymerization,EP)方法制备得到相应的电化学聚合物膜,并对小分子和聚合物的光致(Photoluminescence,PL)和电化学发光(Electrochemiluminescence,ECL)性质进行了研究。3个小分子化合物的溶液、固体以及聚合物均在407~468 nm的蓝光区表现出强的光致发光,在CH_(2)Cl_(2)中的相对荧光量子产率分别为77%、97%和84%。以三丙胺为共反应物,3个化合物的小分子固体薄膜具有一般至良好的ECL,相对量子产率分别为0.52%、55.58%和16.82%。对比发现,化合物2的光致和电化学发光最强,而化合物1的最弱。基于变浓度1H NMR分析,化合物1存在较强的分子间氢键,而化合物2存在较强的分子内氢键,发光效率的差异可能是由分子内和分子间不同氢键作用模式引起的。最后,研究了化合物2的小分子固体薄膜和EP膜在电化学发光检测方面的应用,发现对多巴胺(DA)具有检测性能,最低检出限分别为0.43和1.51μmol/L。Three bis-triphenylamine small molecules 1-3 linked by flexible amides or ester chains were designed and synthesized.The corresponding electrochemical polymer films were prepared by electrochemical polymerization(EP).Following which,the photoluminescence(PL)and electrochemiluminescence(ECL)properties of the small molecules and polymers were studied.The solutions and solids of three small molecules,and their corresponding polymers exhibited strong photoluminescence in the blue region of 407~468 nm.The relative fluorescence quantum yields of compounds 1-3 in CH_(2)Cl_(2) are 77%,97%and 84%,respectively.Using tripropylamine as a co-reactant,the small molecule solid films of the three compounds exhibit general to good ECL with relative quantum yields of 0.52%,55.58%and 16.82%,respectively.Comparative analysis revealed that compound 2 displayed the strongest photoluminescence and electrochemiluminescence,while compound 1 showed the weakest property.Based on the 1H NMR spectroscopic analyses by varying the concentrations,compound 1 exhibits strong intermolecular hydrogen bonding,while compound 2 exhibits strong intramolecular hydrogen bonding.The difference in luminescence efficiency may be caused by different modes of intermolecular and intramolecular hydrogen bonding interactions.Finally,both the small molecule solid film and EP film of compound 2 could be used as an ECL luminophore for detection of dopamine(DA),with a limit of detection(LOD)of 0.43 and 1.51μmol/L,respectively.

关 键 词：双-三苯胺 电化学聚合物膜 光致发光 电化学发光 多巴胺检测 

分 类 号：O625.6[理学—有机化学]