非极性和极性溶剂中 2-(1H-苯并[d]咪唑-2-基)-6-(苯并[d]噻唑-2-基)-4-溴苯酚激发态行为的理论探索

IF 1.6 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Xiaoyi Fu, Jiahe Chen, Qing Wang, Wenjing Xu, Jinfeng Zhao
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引用次数: 0

摘要

鉴于具有潜在双向质子转移(PT)反应通道的新型有机荧光团的潜在意义,本研究主要探讨了新型2-(1h -苯并[d]咪唑-2-基)-6-(苯并[d]-噻唑-2-基)-4-溴苯酚(BIBTB)荧光团的激发态行为。考虑到双向PT通道,我们首先在不同极性的溶剂中检查了羟基指向咪唑和噻唑环的稳定形式。通过在S0状态下扭转二面角(θ1、θ2和θ3),我们理论上验证了在非极性和中极性溶剂中,A结构(羟基指向噻唑环)是最重要的部分,而在极性溶剂中,D结构(羟基指向咪唑环)更为重要。以非极性环己烷(CYC)和极性乙腈(ACE)溶剂为研究对象,比较了氢键的几何变化和红外(IR)振动光谱行为。前沿分子轨道(MOs)引起的电荷重组和预测的氢键能进一步反映了激发态分子内质子转移(ESIPT)的趋势。通过构建势能曲线(PECs)和寻找过渡态(TS)形式,我们证实并阐述了BIBTB荧光团的超快ESIPT机制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Theoretical exploration on excited state behaviors for 2-(1H-benzo[d]imidazole-2-yl)-6-(benzo[d]-thiazol-2-yl)-4-bromophenol in nonpolar and polar solvents

Theoretical exploration on excited state behaviors for 2-(1H-benzo[d]imidazole-2-yl)-6-(benzo[d]-thiazol-2-yl)-4-bromophenol in nonpolar and polar solvents

Given the potential significance of novel organic fluorophores with potential dual-way proton transfer (PT) reaction channels, in this work we mainly focus on probing into the excited state behaviors for the novel 2-(1H-benzo[d]imidazole-2-yl)-6-(benzo[d]-thiazol-2-yl)-4-bromophenol (BIBTB) fluorophore. Given the two-way PT channels, we firstly check the stable form with hydroxyl points to imidazole and thiazole rings in solvents with different polarities. By twisting dihedral angles (θ1, θ2 and θ3) in the S0 state, we theoretically verify that the A form (hydroxyl points to thiazole ring) should be the most important part in nonpolar and moderately polar solvents, while the D structure (hydroxyl points toward imidazole ring) becomes more important in polar solvents. Mainly focusing on nonpolar cyclohexane (CYC) and polar acetonitrile (ACE) solvents, we compare the geometrical changes and infrared (IR) vibrational spectral behaviors related to hydrogen bonds. The charge reorganization resulting from frontier molecular orbitals (MOs) and predicted hydrogen bonding energies further reflects the excited state intramolecular proton transfer (ESIPT) tendency. By constructing potential energy curves (PECs) and searching for transition state (TS) forms, we confirm and expound the ultrafast ESIPT mechanism for the BIBTB fluorophore.

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来源期刊
CiteScore
3.40
自引率
11.10%
发文量
216
审稿时长
7.5 months
期刊介绍: The Journal of the Chinese Chemical Society was founded by The Chemical Society Located in Taipei in 1954, and is the oldest general chemistry journal in Taiwan. It is strictly peer-reviewed and welcomes review articles, full papers, notes and communications written in English. The scope of the Journal of the Chinese Chemical Society covers all major areas of chemistry: organic chemistry, inorganic chemistry, analytical chemistry, biochemistry, physical chemistry, and materials science.
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