BTAP衍生物在不同溶剂中硫代的ESIPT机制的计算探索

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-04-05 DOI:10.1016/j.molliq.2025.127548

Chang Liu, Zibo Shen, Jinfeng Zhao, Wei Hua, Jiahe Chen

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引用次数: 0

摘要

在这项研究中，我们研究了新的3-氨基-5-叔丁基羰基吡咯[3,4- c]吡唑（BTAP）分子，特别是BTAP- oo、BTAP- ss和BTAP- sese化合物，探讨了它们的光诱导行为与碳原子电负性的关系。通过分析这三种具有分子内双键的BTAP衍生物的结构变化、红外（IR）振动、模拟核价分岔（CVB）指数和前沿分子轨道（MOs）的变化，我们发现低原子电负性有利于S1态氢键效应的增强。通过对BTAP- oo、BTAP- ss和BTAP- sese化合物构建的势能面（PESs）的分析，揭示了BTAP化合物即使存在双氢键也表现出激发态分子内质子转移（ESIPT）行为。此外，采用可极化连续统模型（IEFPCM）的积分方程形式，选择乙腈、二氯甲烷和己烷作为溶剂，详细研究了溶剂极性对BTAP衍生物ESIPT行为的影响。研究结果揭示了BTAP衍生物的硫调控ESIPT机制，同时也揭示了BTAP荧光团的极性依赖激发态行为。

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Computational exploration of ESIPT mechanism associated with chalcogen substitutions for BTAP derivatives in different solvents

In this study, we investigated novel 3-amino-5-tert-butoxycarbonyl pyrrole [3,4-C] pyrazole (BTAP) molecules, specifically the BTAP-OO, BTAP-SS, and BTAP-SeSe compounds, exploring their photoinduced behavior in relation to the electronegativity of chalcogen atoms. Through analyzing the structural alterations of these three BTAP derivatives featuring intramolecular double hydrogen bonds, variations in infrared (IR) vibrations, simulated core-valence bifurcation (CVB) indexes, and frontier molecular orbitals (MOs), we observed that low atomic electronegativity favor the enhancement of hydrogen bonding effects in S₁ state. By analyzing the potential energy surfaces (PESs) constructed for BTAP-OO, BTAP-SS, and BTAP-SeSe compounds, we uncovered the excited state intramolecular proton transfer (ESIPT) behavior exhibited by BTAP compounds even dual hydrogen bonds exist. Additionally, employing the Integral Equation Formalism for Polarizable Continuum Model (IEFPCM) and selecting acetonitrile, dichloromethane and hexane as solvents, we conducted a detailed investigation into how solvent polarity influences the ESIPT behavior of BTAP derivatives. The findings revealed the chalcogen-regulated ESIPT mechanism for BTAP derivatives, but also presented the polarity-dependent excited state behaviors for BTAP fluorophore.

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.