Theoretical study on the relationship between ESIPT process and solvent of 9,10-dihydroxybenzo[h]quinolone

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry Pub Date : 2024-10-28 DOI:10.1016/j.jphotochem.2024.116121

Liangyue Cheng, Alexander G. Cherednichenko

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Abstract

To elucidate the relationship between the excited-state intramolecular proton transfer (ESIPT) mechanism of 9,10-dihydroxybenzo[h]quinoline (9-10-HBQ) and the influence of solvents, for better application. This paper focuses on the investigation of hydrogen bond geometric changes, the ESIPT mechanism, and its behavior modulated by solvent polarity. The structural parameters of the ground-state (S₀) and excited-state (S₁) related to the hydrogen bond (O₁H₂⋯O₃), along with the infrared vibrational spectra, core-valence bifurcation (CVB) index, hydrogen bond bond-critical point (BCP) parameters, RDG function isosurfaces, and scatter plots, reveal that the enhanced hydrogen bond strength in the S₁ state promotes the ESIPT behavior of 9-10-HBQ-PT1. Further frontier molecular orbital and natural Population Analysis (NPA) charge analyses indicate that intramolecular charge redistribution facilitates the ESIPT process. Based on the analysis of potential energy curves, transition states (TS), and intrinsic reaction coordinate (IRC) pathways, we found that the reaction energy barriers can be tuned by the solvent. For example, in cyclohexane (Cy), toluene (Tol), chloroform (TCM), and acetonitrile (ACN), the reaction energy barriers were 7.12 kcal/mol, 7.25 kcal/mol, 7.65 kcal/mol, and 8.15 kcal/mol, respectively.

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关于 9,10-二羟基苯并[h]喹啉酮 ESIPT 工艺与溶剂关系的理论研究

为了阐明 9,10-二羟基苯并[h]喹啉（9-10-HBQ）激发态分子内质子转移（ESIPT）机理与溶剂影响之间的关系，以便更好地应用。本文重点研究了氢键几何变化、ESIPT 机理及其受溶剂极性调节的行为。与氢键（O1H2⋯O3）相关的基态（S0）和激发态（S1）的结构参数，以及红外振动光谱、核-价分叉（CVB）指数、氢键临界点（BCP）参数、RDG 函数等值线和散点图显示，S1 状态下氢键强度的增强促进了 9-10-HBQ-PT1 的 ESIPT 行为。进一步的前沿分子轨道和自然群体分析（NPA）电荷分析表明，分子内电荷再分布促进了 ESIPT 过程。根据对势能曲线、过渡态（TS）和固有反应坐标（IRC）途径的分析，我们发现反应能垒可由溶剂调节。例如，在环己烷（Cy）、甲苯（Tol）、氯仿（TCM）和乙腈（ACN）中，反应能垒分别为 7.12 kcal/mol、7.25 kcal/mol、7.65 kcal/mol 和 8.15 kcal/mol。

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来源期刊

Journal of Photochemistry and Photobiology A-chemistry 化学-物理化学

CiteScore

7.90

自引率

7.00%

发文量

580

审稿时长

48 days

期刊介绍： JPPA publishes the results of fundamental studies on all aspects of chemical phenomena induced by interactions between light and molecules/matter of all kinds. All systems capable of being described at the molecular or integrated multimolecular level are appropriate for the journal. This includes all molecular chemical species as well as biomolecular, supramolecular, polymer and other macromolecular systems, as well as solid state photochemistry. In addition, the journal publishes studies of semiconductor and other photoactive organic and inorganic materials, photocatalysis (organic, inorganic, supramolecular and superconductor). The scope includes condensed and gas phase photochemistry, as well as synchrotron radiation chemistry. A broad range of processes and techniques in photochemistry are covered such as light induced energy, electron and proton transfer; nonlinear photochemical behavior; mechanistic investigation of photochemical reactions and identification of the products of photochemical reactions; quantum yield determinations and measurements of rate constants for primary and secondary photochemical processes; steady-state and time-resolved emission, ultrafast spectroscopic methods, single molecule spectroscopy, time resolved X-ray diffraction, luminescence microscopy, and scattering spectroscopy applied to photochemistry. Papers in emerging and applied areas such as luminescent sensors, electroluminescence, solar energy conversion, atmospheric photochemistry, environmental remediation, and related photocatalytic chemistry are also welcome.