基于2,3-二苯基苯并[b]噻吩S,S-二氧化物的AIEgens的自由基介导分子内光环化,Journal of the American Chemical Society

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基于2,3-二苯基苯并[b]噻吩S,S-二氧化物的AIEgens的自由基介导分子内光环化
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-03-30 , DOI: 10.1021/jacs.2c12738
Jingjing Guo _{1,

2} , Jianqing Li ₁ , Tai Wu ₃ , Xiaoluo Peng ₁ , Shihuai Wang ₁ , Zujin Zhao ₁ , Yong Hua ₃ , Ben Zhong Tang ₄ , Yanli Zhao ₂

Affiliation

作为光化学反应的一个重要范畴，光环化被认为是构建智能光响应材料的理想切入点。在此，基于 2,3-二苯基苯并 [ b ] 噻吩S,S开发了一系列具有敏感光响应行为的聚集诱导发光剂 (AIEgens)-dioxide (DP-BTO)，并研究了具有不同电子结构的取代基的影响。综合实验和计算表征表明，它们的光响应活性是由三重态双自由基介导的分子内光环化，然后脱氢产生稳定的多环光产物。这种光环化过程在溶液中活跃，但在固态下受到抑制，因此可以作为激发态的辅助非辐射衰变通道，促进 AIE 效应。此外，光照下产生的三重态双自由基中间体可有效抑制金黄色葡萄球菌的生长，表明它们作为抗菌剂的应用前景广阔。这项工作对 DP-BTO 衍生物的光环化提供了深入的机理描述，并为光化学衰变与光物理性质的相关性提供了一个视角。

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Free Radical-Mediated Intramolecular Photocyclization of AIEgens Based on 2,3-Diphenylbenzo[b]thiophene S,S-Dioxide

As an important category of photochemical reactions, photocyclization is regarded as an ideal entry point for building intelligent photoresponsive materials. Herein, a series of aggregation-induced emission luminogens (AIEgens) with sensitive photoresponsive behavior are developed based on 2,3-diphenylbenzo[b]thiophene S,S-dioxide (DP-BTO), and the impacts of substituents with different electronic structures are investigated. The comprehensive experimental and computational characterizations reveal that their photoresponsive activity is resulted from triplet diradical-mediated intramolecular photocyclization, followed by dehydrogenation to yield stable polycyclic photoproducts. This photocyclization process is active in solution but suppressed in the solid state, and thus can act as a supplementary nonradiative decay channel for the excited state to contribute to AIE effect. Moreover, the generated triplet diradical intermediates upon light irradiation can effectively inhibit the growth of S. aureus, indicative of their promising application as antibacterial agents. This work provides an in-depth mechanistic description about the photocyclization of DP-BTO derivatives and furnishes a perspective on the correlation of photochemical decay and photophysical property.

更新日期：2023-03-30

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