Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior

Metal complexation modulates the antioxidant properties of many flavonoids, including quercetin (QRT). However, competition between the antioxidant and autoxidation processes limits their longevity. This necessitates a deeper understanding of the fate of QRT phenoxy radicals following antioxidant ac...

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Detalles Bibliográficos
Autores: Jena, Subhrakant, Cohen Cohen, Boiko Yuda, Nuncio, Maria Rosaria di, Douhal, Abderrazzak
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Universidad de Castilla-La Mancha
Repositorio:RUIdeRA. Repositorio Institucional de la UCLM
OAI Identifier:oai:ruidera.uclm.es:10578/47921
Acceso en línea:https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202500854
https://hdl.handle.net/10578/47921
Access Level:acceso abierto
Palabra clave:Antioxidants
Flavonoid-metal complex
Ligand to-metal charge transfer
Photochemistry
Time-resolved spectroscopy
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spelling Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond PhotobehaviorJena, SubhrakantCohen Cohen, Boiko YudaNuncio, Maria Rosaria diDouhal, AbderrazzakAntioxidantsFlavonoid-metal complexLigand to-metal charge transferPhotochemistryTime-resolved spectroscopyMetal complexation modulates the antioxidant properties of many flavonoids, including quercetin (QRT). However, competition between the antioxidant and autoxidation processes limits their longevity. This necessitates a deeper understanding of the fate of QRT phenoxy radicals following antioxidant activity. Here, we report on the formation of QRT•Zr complexes and their photobehaviors, which account for the photochemical reactivity of the generated radicals. In methanol, N, N-dimethylformamide, and water, the UV-visible absorption spectra of the 1:1 and 1:2 complexes exhibit a significant bathochromic shift (50–100 nm) and high global binding constants (1 – 14 × 109 M−2). While the formation of charge-transfer states through ligand-to-metal charge transfer in the ground state prevents the excited-state intramolecular proton transfer that typically occurs in QRT, it leads to the generation of excited metal-bound ligand radicals. We present details on the dynamics and further relaxation from femto to millisecond regimes of the excited complexes and generated species. The lifetimes of the formed radicals are considerably shorter than those of the free QRT radicals due to rapid back electron transfer, regenerating the neutral complexes. These findings will facilitate the design of other systems for antioxidant activity, photocatalysis, and various applications in chemistry, biochemistry, and biomedicine.Wiley202620262025info:eu-repo/semantics/articleapplication/pdfhttps://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202500854https://hdl.handle.net/10578/47921reponame:RUIdeRA. Repositorio Institucional de la UCLMinstname:Universidad de Castilla-La ManchaInglés2022-GRIN-34325PRTR-C17MICIU/AEI/10.13039/501100011033info:eu-repo/semantics/openAccessAttribution-NonCommercial-NoDerivs 4.0 Internationalhttps://creativecommons.org/licenses/by-nc-nd/4.0/oai:ruidera.uclm.es:10578/479212026-05-27T07:36:41Z
dc.title.none.fl_str_mv Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
title Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
spellingShingle Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
Jena, Subhrakant
Antioxidants
Flavonoid-metal complex
Ligand to-metal charge transfer
Photochemistry
Time-resolved spectroscopy
title_short Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
title_full Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
title_fullStr Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
title_full_unstemmed Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
title_sort Quercetin•Zirconium Metal Complexes: Insights from Femto to Millisecond Photobehavior
dc.creator.none.fl_str_mv Jena, Subhrakant
Cohen Cohen, Boiko Yuda
Nuncio, Maria Rosaria di
Douhal, Abderrazzak
author Jena, Subhrakant
author_facet Jena, Subhrakant
Cohen Cohen, Boiko Yuda
Nuncio, Maria Rosaria di
Douhal, Abderrazzak
author_role author
author2 Cohen Cohen, Boiko Yuda
Nuncio, Maria Rosaria di
Douhal, Abderrazzak
author2_role author
author
author
dc.subject.none.fl_str_mv Antioxidants
Flavonoid-metal complex
Ligand to-metal charge transfer
Photochemistry
Time-resolved spectroscopy
topic Antioxidants
Flavonoid-metal complex
Ligand to-metal charge transfer
Photochemistry
Time-resolved spectroscopy
description Metal complexation modulates the antioxidant properties of many flavonoids, including quercetin (QRT). However, competition between the antioxidant and autoxidation processes limits their longevity. This necessitates a deeper understanding of the fate of QRT phenoxy radicals following antioxidant activity. Here, we report on the formation of QRT•Zr complexes and their photobehaviors, which account for the photochemical reactivity of the generated radicals. In methanol, N, N-dimethylformamide, and water, the UV-visible absorption spectra of the 1:1 and 1:2 complexes exhibit a significant bathochromic shift (50–100 nm) and high global binding constants (1 – 14 × 109 M−2). While the formation of charge-transfer states through ligand-to-metal charge transfer in the ground state prevents the excited-state intramolecular proton transfer that typically occurs in QRT, it leads to the generation of excited metal-bound ligand radicals. We present details on the dynamics and further relaxation from femto to millisecond regimes of the excited complexes and generated species. The lifetimes of the formed radicals are considerably shorter than those of the free QRT radicals due to rapid back electron transfer, regenerating the neutral complexes. These findings will facilitate the design of other systems for antioxidant activity, photocatalysis, and various applications in chemistry, biochemistry, and biomedicine.
publishDate 2025
dc.date.none.fl_str_mv 2025
2026
2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202500854
https://hdl.handle.net/10578/47921
url https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202500854
https://hdl.handle.net/10578/47921
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv 2022-GRIN-34325
PRTR-C17
MICIU/AEI/10.13039/501100011033
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
Attribution-NonCommercial-NoDerivs 4.0 International
https://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivs 4.0 International
https://creativecommons.org/licenses/by-nc-nd/4.0/
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:RUIdeRA. Repositorio Institucional de la UCLM
instname:Universidad de Castilla-La Mancha
instname_str Universidad de Castilla-La Mancha
reponame_str RUIdeRA. Repositorio Institucional de la UCLM
collection RUIdeRA. Repositorio Institucional de la UCLM
repository.name.fl_str_mv
repository.mail.fl_str_mv
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