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Central Ring Puckering Enhances the Stokes Shift of Xanthene Dyes
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SYSNO ASEP 0583934 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Central Ring Puckering Enhances the Stokes Shift of Xanthene Dyes Author(s) Dunlop, David (UOCHB-X) ORCID
Horváth, P. (CZ)
Klán, P. (CZ)
Slanina, Tomáš (UOCHB-X) ORCID, RID
Šebej, P. (CZ)Article number e202400024 Source Title Chemistry - A European Journal. - : Wiley - ISSN 0947-6539
Roč. 30, č. 19 (2024)Number of pages 7 s. Language eng - English Country DE - Germany Keywords conformation ; fluorescence ; functional dyes ; pyronin ; quantum chemical calculations ; stokes shift ; xanthene OECD category Physical chemistry R&D Projects LTC20076 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Research Infrastructure RECETOX RI II - 90269 - Masarykova univerzita / Přírodovědecká fakulta Method of publishing Open access Institutional support UOCHB-X - RVO:61388963 UT WOS 001162886100001 EID SCOPUS 85185110954 DOI 10.1002/chem.202400024 Annotation Small-molecule dyes are generally designed based on well-understood electronic effects. However, steric hindrance can promote excited-state geometric relaxation, increasing the difference between the positions of absorption and emission bands (the Stokes shift). Accordingly, we hypothesized that sterically induced central ring puckering in xanthene dyes could be used to systematically increase their Stokes shift. Through a combined experimental/quantum-chemical approach, we screened a group of (9-acylimino)-pyronin dyes with a perturbed central ring geometry. Our results showed that an atom with sp(3) hybridization in position 10 of (9-acylimino)-pyronins induces central ring puckering and facilitates excited-state geometric relaxation, thereby markedly enhancing their Stokes shifts (by up to similar to 2000 cm(-1)). Thus, we prepared fluorescent (9-acylimino)-pyronin pH sensors, which showed a Stokes shift disparity between acid and base forms of up to similar to 8700 cm(-1). Moreover, the concept of ring puckering-enhanced Stokes shift can be applied to a wide range of xanthene analogues found in the literature. Therefore, central ring puckering may be reliably used as a strategy for enhancing Stokes shifts in the rational design of dyes. Workplace Institute of Organic Chemistry and Biochemistry Contact asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Year of Publishing 2025 Electronic address https://doi.org/10.1002/chem.202400024
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