Theoretical insights into the excited state hydrogen bond and ESIPT reaction for 2-amino-3-(2’-benzoxazolyl)quinoline and 2-amino-3-(2’-benzothiazolyl)-quinoline

Qiaoli Zhang
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引用次数: 8

Abstract

Two N-H type excited state intramolecular proton transfer (ESIPT) systems (i.e., 2-amino-3-(2’benzoxazolyl)quinoline (ABO) and 2-amino-3-(2’-benzothiazolyl)-quinoline (ABT)) have been investigated. Adopting DFT and TDDFT methods coupling with B3LYP functional and TZVP basis set, our simulations about ABO and ABT molecules have successfully reappeared experimental results, based on which the rationality of our calculations is confirmed. Using Atoms in Molecules (AIM) analytical method, we firstly explore the interactions about chemical bond and verify the formation of hydrogen bond N-H•••N for ABO and ABT in the S0 state. Investigating the primary geometrical parameters involved in N-H•••N, we find it should be strengthened in the S1 state. Upon photoexcitation, charge transfer phenomenon is found via frontier molecular orbitals (MOs), and charge redistribution provides the tendency of ESIPT reaction for ABO and ABT. According to our constructed potential energy curves of both S0 and S1 states for ABO and ABT using two kinds of methods (i.e., the elongation of N-H single bond and the weakening of H•••N hydrogen bond), we clarify the ESIPT mechanisms and explain the recovery of four-level reaction cycle. Our searching transition state (TS) structures and simulated intrinsic reaction coordinate (IRC) path further confirm the ESIPT reaction.
2-氨基-3-(2 ' -苯并恶唑基)喹啉和2-氨基-3-(2 ' -苯并噻唑基)喹啉激发态氢键和ESIPT反应的理论见解
研究了两种N-H型激发态分子内质子转移(ESIPT)体系,即2-氨基-3-(2 ' -苯并恶唑)喹啉(ABO)和2-氨基-3-(2 ' -苯并噻唑)喹啉(ABT)。采用DFT和TDDFT方法,结合B3LYP泛函和TZVP基集,对ABO和ABT分子进行了模拟,成功再现了实验结果,验证了计算的合理性。利用分子中原子(AIM)分析方法,首次探索了ABO和ABT在S0态下化学键的相互作用,并验证了氢键N- h•••N的形成。研究了N- h•••N所涉及的主要几何参数,我们发现它在S1状态下应该得到加强。在光激发作用下,电荷转移现象通过前沿分子轨道(MOs)发生,电荷重分配为ABO和ABT的ESIPT反应提供了趋势。我们利用两种方法(N-H单键的延长和H•••N氢键的减弱)构建了ABO和ABT的S0和S1态势能曲线,阐明了ESIPT的机理,解释了四能级反应循环的恢复。我们对过渡态(TS)结构的搜索和模拟的本征反应坐标(IRC)路径进一步证实了ESIPT反应。
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
Journal of Atomic and Molecular Sciences
Journal of Atomic and Molecular Sciences PHYSICS, ATOMIC, MOLECULAR & CHEMICAL-
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