Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes

Autores
Cadranel, Alejandro; Gravogl, Lisa; Munz, Dominik; Meyer, Karsten
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report high-valent iron complexes supported by N-heterocyclic carbene (NHC)-anchored, bis-phenolate pincer ligands that undergo ligand-to-metal charge transfer (LMCT) upon photoexcitation. The resulting excited states – with a lifetime in the picosecond range – feature a ligand-based, mixed-valence system and intense intervalence charge transfer bands in the near-infrared region. Upon oxidation of the complex, corresponding intervalence charge transfer absorptions are also observed in the ground state. We suggest that the spectroscopic hallmarks of such LMCT states provide useful tools to decipher excited-state decay mechanisms in high-valent NHC complexes. Our observations further indicate that NHC-anchored, bis-phenolate pincer ligands are not sufficiently strong donors to prevent the population of excited metal-centered states in high-valent iron complexes.
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
Fil: Gravogl, Lisa. Universitat Erlangen-Nuremberg; Alemania
Fil: Munz, Dominik. Universitat Erlangen-Nuremberg; Alemania
Fil: Meyer, Karsten. Universitat Erlangen-Nuremberg; Alemania
Materia
IRON N-HETEROCYCLIC CARBENE COMPLEXES
IRON PHENOLATE COMPLEXES
LMCT EXCITED STATE
PHOTOINDUCED MIXED VALENCY
ULTRAFAST SPECTROSCOPY
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/210261
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene ComplexesCadranel, AlejandroGravogl, LisaMunz, DominikMeyer, KarstenIRON N-HETEROCYCLIC CARBENE COMPLEXESIRON PHENOLATE COMPLEXESLMCT EXCITED STATEPHOTOINDUCED MIXED VALENCYULTRAFAST SPECTROSCOPYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report high-valent iron complexes supported by N-heterocyclic carbene (NHC)-anchored, bis-phenolate pincer ligands that undergo ligand-to-metal charge transfer (LMCT) upon photoexcitation. The resulting excited states – with a lifetime in the picosecond range – feature a ligand-based, mixed-valence system and intense intervalence charge transfer bands in the near-infrared region. Upon oxidation of the complex, corresponding intervalence charge transfer absorptions are also observed in the ground state. We suggest that the spectroscopic hallmarks of such LMCT states provide useful tools to decipher excited-state decay mechanisms in high-valent NHC complexes. Our observations further indicate that NHC-anchored, bis-phenolate pincer ligands are not sufficiently strong donors to prevent the population of excited metal-centered states in high-valent iron complexes.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; ArgentinaFil: Gravogl, Lisa. Universitat Erlangen-Nuremberg; AlemaniaFil: Munz, Dominik. Universitat Erlangen-Nuremberg; AlemaniaFil: Meyer, Karsten. Universitat Erlangen-Nuremberg; AlemaniaWiley VCH Verlag2022-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/210261Cadranel, Alejandro; Gravogl, Lisa; Munz, Dominik; Meyer, Karsten; Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes; Wiley VCH Verlag; Chemistry- A European Journal; 28; 41; 3-2022; 1-90947-6539CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/10.1002/chem.202200269info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202200269info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:48:00Zoai:ri.conicet.gov.ar:11336/210261instacron: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:34982025-09-03 09:48:00.214CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
title Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
spellingShingle Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
Cadranel, Alejandro
IRON N-HETEROCYCLIC CARBENE COMPLEXES
IRON PHENOLATE COMPLEXES
LMCT EXCITED STATE
PHOTOINDUCED MIXED VALENCY
ULTRAFAST SPECTROSCOPY
title_short Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
title_full Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
title_fullStr Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
title_full_unstemmed Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
title_sort Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes
dc.creator.none.fl_str_mv Cadranel, Alejandro
Gravogl, Lisa
Munz, Dominik
Meyer, Karsten
author Cadranel, Alejandro
author_facet Cadranel, Alejandro
Gravogl, Lisa
Munz, Dominik
Meyer, Karsten
author_role author
author2 Gravogl, Lisa
Munz, Dominik
Meyer, Karsten
author2_role author
author
author
dc.subject.none.fl_str_mv IRON N-HETEROCYCLIC CARBENE COMPLEXES
IRON PHENOLATE COMPLEXES
LMCT EXCITED STATE
PHOTOINDUCED MIXED VALENCY
ULTRAFAST SPECTROSCOPY
topic IRON N-HETEROCYCLIC CARBENE COMPLEXES
IRON PHENOLATE COMPLEXES
LMCT EXCITED STATE
PHOTOINDUCED MIXED VALENCY
ULTRAFAST 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 We report high-valent iron complexes supported by N-heterocyclic carbene (NHC)-anchored, bis-phenolate pincer ligands that undergo ligand-to-metal charge transfer (LMCT) upon photoexcitation. The resulting excited states – with a lifetime in the picosecond range – feature a ligand-based, mixed-valence system and intense intervalence charge transfer bands in the near-infrared region. Upon oxidation of the complex, corresponding intervalence charge transfer absorptions are also observed in the ground state. We suggest that the spectroscopic hallmarks of such LMCT states provide useful tools to decipher excited-state decay mechanisms in high-valent NHC complexes. Our observations further indicate that NHC-anchored, bis-phenolate pincer ligands are not sufficiently strong donors to prevent the population of excited metal-centered states in high-valent iron complexes.
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
Fil: Gravogl, Lisa. Universitat Erlangen-Nuremberg; Alemania
Fil: Munz, Dominik. Universitat Erlangen-Nuremberg; Alemania
Fil: Meyer, Karsten. Universitat Erlangen-Nuremberg; Alemania
description We report high-valent iron complexes supported by N-heterocyclic carbene (NHC)-anchored, bis-phenolate pincer ligands that undergo ligand-to-metal charge transfer (LMCT) upon photoexcitation. The resulting excited states – with a lifetime in the picosecond range – feature a ligand-based, mixed-valence system and intense intervalence charge transfer bands in the near-infrared region. Upon oxidation of the complex, corresponding intervalence charge transfer absorptions are also observed in the ground state. We suggest that the spectroscopic hallmarks of such LMCT states provide useful tools to decipher excited-state decay mechanisms in high-valent NHC complexes. Our observations further indicate that NHC-anchored, bis-phenolate pincer ligands are not sufficiently strong donors to prevent the population of excited metal-centered states in high-valent iron complexes.
publishDate 2022
dc.date.none.fl_str_mv 2022-03
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/11336/210261
Cadranel, Alejandro; Gravogl, Lisa; Munz, Dominik; Meyer, Karsten; Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes; Wiley VCH Verlag; Chemistry- A European Journal; 28; 41; 3-2022; 1-9
0947-6539
CONICET Digital
CONICET
url http://hdl.handle.net/11336/210261
identifier_str_mv Cadranel, Alejandro; Gravogl, Lisa; Munz, Dominik; Meyer, Karsten; Intense Photoinduced Intervalence Charge Transfer in High-Valent Iron Mixed Phenolate/Carbene Complexes; Wiley VCH Verlag; Chemistry- A European Journal; 28; 41; 3-2022; 1-9
0947-6539
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://onlinelibrary.wiley.com/doi/10.1002/chem.202200269
info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.202200269
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv 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
_version_ 1842268895716573184
score 13.13397

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