Deciphering solvent-driven intra- and intermolecular excited-state proton transfer mechanisms in 3BTHMB via TDDFT

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-10-04 DOI:10.1016/j.comptc.2025.115529

Jiaan Gao, Xiaotong Guan, Siqi Wang, Yifu Zhang, Hui Li, Guangyong Jin

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Abstract

The excited-state proton transfer (ESPT) process and photophysical properties of 3BTHMB molecule with different solvents are systematically studied via the density functional theory (DFT) and time-dependent DFT (TDDFT) methodologies. Our research confirms that the 3BTHMB molecule undergoes the excited state intramolecular proton transfer (ESItrPT) process in HEX and THF. In HEX, ESItrPT process is accompanied by the Twisted intramolecular charge transfer (TICT) process, and TICT is the cause of fluorescence attenuation. In THF, the observed short-wavelength emission originates from the Enol* state, whereas the ESItrPT-induced fluorescence from the Keto* state accounts for the long-wavelength emission. In DMF and MeOH, the molecule forms IEHB with the solvent. Under photoexcitation, we observe a strengthening of IEHBs in DMF, while in MeOH, this interaction is diminished. Importantly, despite the solvent-dependent modulations in IEHB strength, these interactions consistently facilitate the excited state intermolecular proton transfer (ESIerPT) process. This work provides a detailed understanding of the distinct photophysical behaviors of 3BTHMB in various solvents, offering valuable insights for experimental studies on efficient fluorescent probes for ESPT activity.

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通过TDDFT解读3BTHMB中溶剂驱动的分子内和分子间激发态质子转移机制

采用密度泛函理论（DFT）和时间依赖DFT （TDDFT）方法系统研究了3BTHMB分子在不同溶剂中的激发态质子转移（ESPT）过程和光物理性质。我们的研究证实了3BTHMB分子在HEX和THF中经历激发态分子内质子转移（ESItrPT）过程。在HEX中，ESItrPT过程伴随着分子内电荷转移（Twisted intrarmolecular charge transfer， TICT）过程，而TICT是荧光衰减的原因。在THF中，观察到的短波发射来自Enol*态，而esitrpt诱导的Keto*态荧光是长波发射的原因。在DMF和MeOH中，分子与溶剂形成IEHB。在光激发下，我们观察到DMF中的IEHBs增强，而在MeOH中，这种相互作用减弱。重要的是，尽管IEHB强度存在溶剂依赖性调节，但这些相互作用始终促进激发态分子间质子转移（ESIerPT）过程。这项工作提供了对3BTHMB在各种溶剂中的独特光物理行为的详细了解，为高效荧光探针ESPT活性的实验研究提供了有价值的见解。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.