Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid

Solar fuel generation relies on the catalysis of multielectron, multiproton reactions facilitated in nature by charge accumulation in electron relays like NADPH or hydroquinone. Here, we demonstrate the light-driven charge accumulation in a noble-metal-free photochemical dyad comprising a bodipy pho...

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Autores: Cariño, Christian, Moussa, Naguy, Blanchard, Sébastien, Solé-Daura, Albert, Proust, Anna, Izzet, Guillaume
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/487034
Acceso en línea:http://hdl.handle.net/2072/487034
https://doi.org/10.1039/D5QI01202C
Access Level:acceso embargado
Palabra clave:Química
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spelling Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybridCariño, ChristianMoussa, NaguyBlanchard, SébastienSolé-Daura, AlbertProust, AnnaIzzet, GuillaumeQuímica54Solar fuel generation relies on the catalysis of multielectron, multiproton reactions facilitated in nature by charge accumulation in electron relays like NADPH or hydroquinone. Here, we demonstrate the light-driven charge accumulation in a noble-metal-free photochemical dyad comprising a bodipy photosensitizer linked to a Dawson polyoxometalate (POM) using triethylamine (TEA) as sacrificial electron donor. Under visible light irradiation, the hybrid dyad accumulates up to two electrons on the POM, achieving complete conversion within few minutes. The first reduction proceeds rapidly and efficiently while the second electron is introduced more slowly through an intricate, multi-pathway mechanism that we inferred through combined spectroscopy, electrochemistry and theoretical calculations. The formation of the two-electron reduced species is enhanced in the presence of trifluoroacetic acid by virtue of proton-coupled electron transfer (PCET) as well as by promoting the dismutation of the one-electron reduced POM. Simultaneously, POM reduction may also take place via a light-independent route involving the reactive TEA radical byproduct, effectively rendering TEA an overall two-electron, one-proton donor. The stored redox equivalents in the POM were demonstrated to activate oxygen but also to be engaged in PCET to substrates such as 1,4-benzoquinone, highlighting the potential utility of POM–photosensitizer hybrids in solar fuel-related transformations.info:eu-repo/semantics/acceptedVersionRSC2025info:eu-repo/semantics/article10 p.application/pdfhttp://hdl.handle.net/2072/487034https://doi.org/10.1039/D5QI01202CRECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésC.C. acknowledges the Ministère de l’Enseignement Supérieur et de la Recherche (MESR, France) for his Ph.D. fellowship.A.S.- D. acknowledges financial support from the “la Caixa” Foundation (ID 100010434) under the fellowship code LCF/BQ/PI24/12040012Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/embargoedAccessoai:recercat.cat:2072/4870342026-05-29T05:05:01Z
dc.title.none.fl_str_mv Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
title Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
spellingShingle Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
Cariño, Christian
Química
54
title_short Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
title_full Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
title_fullStr Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
title_full_unstemmed Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
title_sort Insights into the intricate charge photoaccumulation in a polyoxometalate–bodipy covalent hybrid
dc.creator.none.fl_str_mv Cariño, Christian
Moussa, Naguy
Blanchard, Sébastien
Solé-Daura, Albert
Proust, Anna
Izzet, Guillaume
author Cariño, Christian
author_facet Cariño, Christian
Moussa, Naguy
Blanchard, Sébastien
Solé-Daura, Albert
Proust, Anna
Izzet, Guillaume
author_role author
author2 Moussa, Naguy
Blanchard, Sébastien
Solé-Daura, Albert
Proust, Anna
Izzet, Guillaume
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Química
54
topic Química
54
description Solar fuel generation relies on the catalysis of multielectron, multiproton reactions facilitated in nature by charge accumulation in electron relays like NADPH or hydroquinone. Here, we demonstrate the light-driven charge accumulation in a noble-metal-free photochemical dyad comprising a bodipy photosensitizer linked to a Dawson polyoxometalate (POM) using triethylamine (TEA) as sacrificial electron donor. Under visible light irradiation, the hybrid dyad accumulates up to two electrons on the POM, achieving complete conversion within few minutes. The first reduction proceeds rapidly and efficiently while the second electron is introduced more slowly through an intricate, multi-pathway mechanism that we inferred through combined spectroscopy, electrochemistry and theoretical calculations. The formation of the two-electron reduced species is enhanced in the presence of trifluoroacetic acid by virtue of proton-coupled electron transfer (PCET) as well as by promoting the dismutation of the one-electron reduced POM. Simultaneously, POM reduction may also take place via a light-independent route involving the reactive TEA radical byproduct, effectively rendering TEA an overall two-electron, one-proton donor. The stored redox equivalents in the POM were demonstrated to activate oxygen but also to be engaged in PCET to substrates such as 1,4-benzoquinone, highlighting the potential utility of POM–photosensitizer hybrids in solar fuel-related transformations.
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/487034
https://doi.org/10.1039/D5QI01202C
url http://hdl.handle.net/2072/487034
https://doi.org/10.1039/D5QI01202C
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv C.C. acknowledges the Ministère de l’Enseignement Supérieur et de la Recherche (MESR, France) for his Ph.D. fellowship.
A.S.- D. acknowledges financial support from the “la Caixa” Foundation (ID 100010434) under the fellowship code LCF/BQ/PI24/12040012
dc.rights.none.fl_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/embargoedAccess
rights_invalid_str_mv Attribution 4.0 International
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv embargoedAccess
dc.format.none.fl_str_mv 10 p.
application/pdf
dc.publisher.none.fl_str_mv RSC
publisher.none.fl_str_mv RSC
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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