Multistimuli‐Responsive Chromism of Vinylene‐Linked Bisflavin Based on the Aggregation and Redox Properties
Multistimuli‐Responsive Chromism of Vinylene‐Linked Bisflavin Based on the Aggregation and Redox Properties
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基于聚集和氧化还原性质的亚乙烯基连接双黄素的多刺激响应变色
DOI：
10.1002/chem.202202257
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Naota Takeshi
中科院分区：
文献类型：
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作者：
Kawamorita Soichiro;Li Zimeng;Okamoto Koyo;Naota Takeshi
观察到具有扩展的 π 共轭平台的亚乙烯基连接的双黄素 1 a 具有多刺激响应变色现象。在 298 K 紫外激发下观察到的 CHCl3 稀溶液（0.2 mM）的黄色发射在（1）浓度增加、（2）温度降低和（3）溶剂变化时变为橙色或红色发射。这与 N-甲基化双黄素类似物 1 频带单黄素 2 的几乎非刺激响应变色形成鲜明对比。在各种条件下通过 1 H NMR 分析进行的机理研究表明，扩展的 π 共轭平台和 1 代酰亚胺部分在低序和高序聚集体的形成中具有可控性，这会导致发射颜色随变化而变化。双黄素1 a也表现出氧化还原诱导的变色，其中1 的橙色发射在厌氧条件下通过添加肼而被猝灭，并在随后通入氧气后变回原始发射。
Multistimuli‐responsive chromism was observed for vinylene‐linked bisflavin1 awith an extended π‐conjugated platform. The yellow emission of a dilute solution of1 ain CHCl3(0.2 mM) observed at 298 K under UV excitation was changed to orange or red emission upon (1) an increase of concentration, (2) a decrease of temperature, and (3) variation of the solvent. This is in contrast to the almost non stimuli‐responsive chromism of theN‐methylated bisflavin analogue1 band monoflavin2 a. Mechanistic investigation by1H NMR analysis under various conditions revealed that the extended π‐conjugation platform and imide moiety of1 agenerate controllability in the formation of lower‐ and higher‐ordered aggregates, which induce variation of the emission color upon change. Bisflavin1 aalso exhibited redox‐induced chromism, where the orange emission of1 awas quenched by the addition of hydrazine under anaerobic conditions, and changed back to the original emission upon subsequent bubbling of O2gas.