Blockade of persistent colored isomer formation in photochromic 3H-naphthopyrans by excited-state intramolecular proton transfer
Persistent URL
Author(s)
Gierczyk, Błażej
Murphree, S. Shaun
Rode, Michal F.
Burdzinski, Gotard
Date Issued
November 10, 2022
Abstract
In photochemistry the excited-state intramolecular proton transfer process (ESIPT) is often observed as a highly efficient singlet excited state depletion pathway, which in the presence of a strong intramolecular hydrogen bond may proceed on a subpicosecond time scale. The present work describes the suppression of unwanted transoid-trans isomer formation in photochromic 3H-naphthopyran derivatives by the introduction of a 5-hydroxy substituent. According to time-resolved spectroscopy experiments and excited-state ab initio calculations, transoid-cis → transoid-trans photoisomerization is reduced by a competitive ESIPT channel in nonpolar solvent (cyclohexane). Upon specific solute–solvent interactions (methanol, acetonitrile) the intramolecular hydrogen bond in the transoid-cis form is perturbed, favoring the internal conversion S₁ → S₀ process as photostabilizing channel.
Journal
Scientific Reports
Department
Chemistry
Citation
Gierczyk, B., Murphree, S.S., Rode, M.F. et al. Blockade of persistent colored isomer formation in photochromic 3H-naphthopyrans by excited-state intramolecular proton transfer. Sci Rep 12, 19159 (2022). https://doi.org/10.1038/s41598-022-23759-9
Publisher
Nature Portfolio
Version of Article
Published article
DOI
10.1038/s41598-022-23759-9
ISSN
2045-2322
Rights
© The Author(s) 2022. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
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