The alkoxylation effects on the excited-state intramolecular proton transfer behaviors for 2,6-bis(benzothiazolyl-2-yl)phenol fluorophore: A theoretical research,Journal of Physical Organic Chemistry

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The alkoxylation effects on the excited-state intramolecular proton transfer behaviors for 2,6-bis(benzothiazolyl-2-yl)phenol fluorophore: A theoretical research
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2022-03-21 , DOI: 10.1002/poc.4341
Lijuan Shi ₁ , Dapeng Yang ₂

Affiliation

Given the unique luminescent properties, the excited-state intramolecular proton transfer (ESIPT) materials have attracted lots of eyes in recent years. In view of the promising highly efficient red-emitting material, the 2,6-bis(benzothiazolyl-2-yl)phenol (DBTP) under alkoxy groups at the 4-position reveals important properties. In this work, modification of DBTP fluorophore, that is, DBTP-OMe (methoxy), DBTP-OEt (ethoxy), DBTP-OPr (propoxy), and DBTP-OBt (butoxy) derivatives, have been explored theoretically. Based on the analyses of chemical structural variations and infrared (IR) vibrational spectra in both S₀ and S₁ states, the enhanced intramolecular hydrogen bonding interactions could be clearly found, which will promote the ESIPT tendency. Particularly, the DBTP-OMe with stronger hydrogen bond reveals the easier PT tendency upon photo-induced excitation. Paying attention to the changes of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), it could be found the charge transfer happens in the excited-state molecules, and the reorganization of charge densities should be conducive to promoting the ESIPT process. Simulated potential energy curves indicated the ultrafast ESIPT reaction occurs for DBTP-OMe, DBTP-OEt, DBTP-OPr, and DBTP-OBt derivatives. The searched transition state (TS) structures in S₁-state reaction path suggested the derivatives with few alkyl groups might be more probe to occur the ESIPT reaction than the more alkyl ones for DBTP system.

中文翻译：

烷氧基化对 2,6-双（苯并噻唑基-2-基）苯酚荧光团激发态分子内质子转移行为的影响：一项理论研究

鉴于独特的发光特性，激发态分子内质子转移（ESIPT）材料近年来吸引了很多人的目光。鉴于有前景的高效发红光材料，4位烷氧基下的2,6-双（苯并噻唑基-2-基）苯酚（DBTP）显示出重要的性质。在这项工作中，从理论上探讨了 DBTP 荧光团的修饰，即 DBTP-OMe（甲氧基）、DBTP-OEt（乙氧基）、DBTP-OPr（丙氧基）和 DBTP-OBt（丁氧基）衍生物。基于对 S ₀和 S _{1中的化学结构变化和红外 (IR) 振动光谱的分析}状态，可以清楚地发现增强的分子内氢键相互作用，这将促进ESIPT趋势。特别是，具有更强氢键的 DBTP-OMe 在光诱导激发下显示出更容易的 PT 趋势。关注最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）的变化，可以发现电荷转移发生在激发态分子中，电荷密度的重组应该有利于促进ESIPT过程。模拟的势能曲线表明，DBTP-OMe、DBTP-OEt、DBTP-OPr 和 DBTP-OBt 衍生物发生超快 ESIPT 反应。_{S 1}中搜索到的过渡态 (TS) 结构态反应路径表明，对于 DBTP 体系，具有较少烷基的衍生物可能比具有更多烷基的衍生物更容易发生 ESIPT 反应。

更新日期：2022-03-21

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