Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores

Autores
Cotic, Agustina Ludmila; Heinemann, Frank W.; Slep, Leonardo Daniel; Cadranel, Alejandro
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2’-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.
Fil: Cotic, Agustina Ludmila. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Heinemann, Frank W.. Universitat Erlangen-Nuremberg; Alemania
Fil: Slep, Leonardo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Cadranel, Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Materia
Dissipation
Energy Conversion
Artificial Photosynthesis
Unltrafast Spectroscopy
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/264702
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} ChromophoresCotic, Agustina LudmilaHeinemann, Frank W.Slep, Leonardo DanielCadranel, AlejandroDissipationEnergy ConversionArtificial PhotosynthesisUnltrafast Spectroscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2’-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.Fil: Cotic, Agustina Ludmila. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Heinemann, Frank W.. Universitat Erlangen-Nuremberg; AlemaniaFil: Slep, Leonardo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Cadranel, Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaWiley VCH Verlag2024-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/264702Cotic, Agustina Ludmila; Heinemann, Frank W.; Slep, Leonardo Daniel; Cadranel, Alejandro; Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores; Wiley VCH Verlag; Chemphyschem; 25; 14; 4-2024; 1-91439-4235CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cphc.202400246info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.202400246info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:47:34Zoai:ri.conicet.gov.ar:11336/264702instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:47:35.02CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
title Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
spellingShingle Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
Cotic, Agustina Ludmila
Dissipation
Energy Conversion
Artificial Photosynthesis
Unltrafast Spectroscopy
title_short Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
title_full Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
title_fullStr Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
title_full_unstemmed Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
title_sort Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores
dc.creator.none.fl_str_mv Cotic, Agustina Ludmila
Heinemann, Frank W.
Slep, Leonardo Daniel
Cadranel, Alejandro
author Cotic, Agustina Ludmila
author_facet Cotic, Agustina Ludmila
Heinemann, Frank W.
Slep, Leonardo Daniel
Cadranel, Alejandro
author_role author
author2 Heinemann, Frank W.
Slep, Leonardo Daniel
Cadranel, Alejandro
author2_role author
author
author
dc.subject.none.fl_str_mv Dissipation
Energy Conversion
Artificial Photosynthesis
Unltrafast Spectroscopy
topic Dissipation
Energy Conversion
Artificial Photosynthesis
Unltrafast Spectroscopy
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2’-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.
Fil: Cotic, Agustina Ludmila. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Heinemann, Frank W.. Universitat Erlangen-Nuremberg; Alemania
Fil: Slep, Leonardo Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Cadranel, Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
description In MLCT chromophores, internal conversion (IC) in the form of hole reconfiguration pathways (HR) is a major source of dissipation of the absorbed photon energy. Therefore, it is desirable to minimize their impact in energy conversion schemes by slowing them down. According to previous findings on {Ru(bpy)} chromophores, donor-acceptor interactions between the Ru ion and the ligand scaffold might allow to control HR/IC rates. Here, a series of [Ru(tpm)(bpy)(R-py)]2+ chromophores, where tpm is tris(1-pyrazolyl)methane, bpy is 2,2’-bipyridine and R-py is a 4-substituted pyridine, were prepared and fully characterized employing electrochemistry, spectroelectrochemistry, steady-state absorption/emission spectroscopy and electronic structure computations based on DFT/TD-DFT. Their excited-state decay was monitored using nanosecond and femtosecond transient absorption spectroscopy. HR/IC lifetimes as slow as 568 ps were obtained in DMSO at room temperature, twice as slow as in the reference species [Ru(tpm)(bpy)(NCS)]+.
publishDate 2024
dc.date.none.fl_str_mv 2024-04
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/264702
Cotic, Agustina Ludmila; Heinemann, Frank W.; Slep, Leonardo Daniel; Cadranel, Alejandro; Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores; Wiley VCH Verlag; Chemphyschem; 25; 14; 4-2024; 1-9
1439-4235
CONICET Digital
CONICET
url http://hdl.handle.net/11336/264702
identifier_str_mv Cotic, Agustina Ludmila; Heinemann, Frank W.; Slep, Leonardo Daniel; Cadranel, Alejandro; Influence of Donor‐Acceptor Interactions on MLCT Hole Reconfiguration in {Ru(bpy)} Chromophores; Wiley VCH Verlag; Chemphyschem; 25; 14; 4-2024; 1-9
1439-4235
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cphc.202400246
info:eu-repo/semantics/altIdentifier/doi/10.1002/cphc.202400246
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.982451

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