Theoretical Unveiling Photoinduced Excited State Behaviors for BP(OH)₂DCEt₂ Fluorophore: Effects of Solvent Polarity.

IF 2.7 2区化学 Q3 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry A Pub Date : 2025-05-28 DOI:10.1021/acs.jpca.5c02523

Zibo Shen, Chang Liu, Jinfeng Zhao, Jiahe Chen

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引用次数: 0

Abstract

In this work, the influence of solvent polarities on the excited-state intramolecular proton transfer (ESIPT) process of BP(OH)₂DCEt₂ fluorophore has been systematically investigated in three solvents with distinct polarities (acetonitrile, chloroform, and cyclohexane) through DFT and TDDFT methodologies. We mainly focus on elucidating the related excited-state double proton transfer (ESDPT) mechanism in BP(OH)₂DCEt₂. We analyze geometric configurations, infrared (IR) vibrational spectra, and core-valence bifurcation (CVB) indexes to verify the enhancement of the dual hydrogen bonds in the excited state. Meanwhile, we detected the HOMO and LUMO orbitals to investigate the effects of charge redistribution on the ESIPT/ESDPT process. The reactional potential energy surfaces (PESs) are scanned and transition state (TS) forms are searched to testify the stepwise ESDPT mechanism for BP(OH)₂DCEt₂ systems in three solvents. We also propose that the increase of solvent polarity can promote the occurrence of the step-by-step ESDPT reaction processes for the BP(OH)₂DCEt₂ system based on the calculated S₁-state potential energy barriers in the surrounding environment.

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BP(OH)2DCEt2荧光团光致激发态行为的理论揭示：溶剂极性的影响。

本研究采用DFT和TDDFT方法，系统研究了溶剂极性对BP(OH)2DCEt2荧光团激发态质子转移（ESIPT）过程的影响，溶剂极性分别为乙腈、氯仿和环己烷。本文主要研究了BP(OH)2DCEt2的激发态双质子转移（ESDPT）机制。我们分析了几何构型、红外（IR）振动光谱和核价分岔（CVB）指数来验证激发态下双氢键的增强。同时，我们检测了HOMO和LUMO轨道，研究了电荷重分配对ESIPT/ESDPT过程的影响。通过扫描反应势能面（PESs）和寻找过渡态（TS）形式来证明BP(OH)2DCEt2体系在三种溶剂中的逐步ESDPT机制。基于周围环境中s1态势垒的计算，我们还提出溶剂极性的增加可以促进BP(OH)2DCEt2体系逐步发生ESDPT反应过程。

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

The Journal of Physical Chemistry A 化学-物理：原子、分子和化学物理

CiteScore

5.20

自引率

10.30%

发文量

922

审稿时长

1.3 months

期刊介绍： The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.