{"title":"Insight into solvation-regulated emission: Dissecting the switchable ESIPT/ESPT mechanisms in HNT molecule","authors":"","doi":"10.1016/j.jphotochem.2024.116124","DOIUrl":null,"url":null,"abstract":"<div><div>As a crucial physical and chemical process, excited-state proton transfer has garnered significant interest among researchers due to its broad applications in photobiology. Recently, Wu et al. synthesized 3-(benzo[d]thiazol-2-yl) naphthalene-2-ol (HNT) molecule that exhibits excited-state intramolecular proton transfer (ESIPT) characteristic in THF while undergoes excited-state intermolecular proton transfer (ESPT) in aqueous solvent, which induce its solvent-regulated emission nature [Dyes and Pigments 182 (2020) 108665]. However, the dynamic interactions between the proton transfer mechanisms and the emission properties of the HNT molecule are yet to be fully elucidated. Specifically, the role of solvation effects in regulating inter- and intramolecular proton transfer, which leads to modifications in fluorescence properties, should be in-depth considered. In the present work, we delved into the ESIPT dynamics of the HNT molecule in aprotic THF, and examined the ESPT in protic aqueous solvent. Our findings indicate that the ESIPT process promotes the intersystem crossing process, which diminishes Keto* emission in THF solvent. Furthermore, the ESPT process within the HNT-water cluster accounts for the observed dual-fluorescence in aqueous solvent. This research illuminates the role of solute–solvent interactions in affecting the ESIPT/ESPT pathways, thereby clarifying the nature of HNT emission and providing an advantageous methodology for engineering novel dyes with customizable fluorescence characteristics.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":null,"pages":null},"PeriodicalIF":4.1000,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Photochemistry and Photobiology A-chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1010603024006683","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
As a crucial physical and chemical process, excited-state proton transfer has garnered significant interest among researchers due to its broad applications in photobiology. Recently, Wu et al. synthesized 3-(benzo[d]thiazol-2-yl) naphthalene-2-ol (HNT) molecule that exhibits excited-state intramolecular proton transfer (ESIPT) characteristic in THF while undergoes excited-state intermolecular proton transfer (ESPT) in aqueous solvent, which induce its solvent-regulated emission nature [Dyes and Pigments 182 (2020) 108665]. However, the dynamic interactions between the proton transfer mechanisms and the emission properties of the HNT molecule are yet to be fully elucidated. Specifically, the role of solvation effects in regulating inter- and intramolecular proton transfer, which leads to modifications in fluorescence properties, should be in-depth considered. In the present work, we delved into the ESIPT dynamics of the HNT molecule in aprotic THF, and examined the ESPT in protic aqueous solvent. Our findings indicate that the ESIPT process promotes the intersystem crossing process, which diminishes Keto* emission in THF solvent. Furthermore, the ESPT process within the HNT-water cluster accounts for the observed dual-fluorescence in aqueous solvent. This research illuminates the role of solute–solvent interactions in affecting the ESIPT/ESPT pathways, thereby clarifying the nature of HNT emission and providing an advantageous methodology for engineering novel dyes with customizable fluorescence characteristics.
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.