Insight into solvent-polarity-regulated photoinduced excited state behaviors for E-HBT fluorophore: a theoretical investigation

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2024-01-12 DOI:10.1007/s00214-023-03086-6

Chaozheng Li, Hao Dong, Rivaille Liu

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Abstract

Inspired by the remarkable photochemical and photophysical properties of novel 2-(2′-hydroxyphenyl)benzothiazole (HBT) derivatives that could be potentially applied across various disciplines, in this work, effects of solvent polarity on excited state hydrogen bond effects and excited state intramolecular proton transfer (ESIPT) reaction of 5-{2-[2-(4-amino-phenyl)-2,3-dihydro-benzofuran-6-yl]-vinyl}-2-benzothiazol-2-yl-phenol (E-HBT) are focused. By comparing the structural changes and infrared (IR) vibrational spectra of the E-HBT fluorophore in polar acetonitrile, moderate polar dichloromethane and nonpolar cyclohexane solvents, combined with the preliminary detection of hydrogen bond interaction by core-valence bifurcation (CVB) index, we can conclude that the hydrogen bond could be strengthened in S₁ state, which is favorable for the occurrence of ESIPT reactions. The charge recombination behavior of hydrogen bond induced by photoexcitation also further illustrates this point. Via constructing potential energy curves (PECs) based on restrictive optimization and searching transition state (TS) form, we confirm change of surrounding solvent polarity has a regulatory effect on the ESIPT behavior for E-HBT, that is, the higher the polarity of the solvent, the more favorable it is for the ESIPT reaction.

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洞察 E-HBT 荧光体受溶剂极性调节的光诱导激发态行为：一项理论研究

新型 2-(2′-羟基苯基)苯并噻唑（HBT）衍生物具有显著的光化学和光物理性质，可应用于多个学科，受此启发，本研究开展了以下工作、溶剂极性对 5-{2-[2-(4-氨基苯基)-2,3-二氢苯并呋喃-6-基]-乙烯基}-2-苯并噻唑-2-基-苯酚（E-HBT）的激发态氢键效应和激发态分子内质子转移（ESIPT）反应的影响。通过比较 E-HBT 荧光体在极性乙腈、中等极性二氯甲烷和非极性环己烷溶剂中的结构变化和红外振动光谱，结合核价分叉（CVB）指数对氢键相互作用的初步检测，我们可以得出结论：氢键在 S1 状态下会得到加强，有利于 ESIPT 反应的发生。光激发诱导氢键的电荷重组行为也进一步说明了这一点。通过构建基于限制性优化的势能曲线（PEC）和寻找过渡态（TS）形式，我们证实了周围溶剂极性的变化对 E-HBT 的 ESIPT 行为具有调节作用，即溶剂极性越高，越有利于 ESIPT 反应的发生。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.