Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants

Autores
Wolcan, Ezequiel
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We review the morphological and the photophysical properties of several inorganic polymers that can be prepared from poly-4- vinylpyridine (P4VP). These polymers contain –Re(CO)3 (N^ N)+ pendants attached to their backbone with α-diimine ligands (N^ N) such as 2,2´-bipyridine (bpy), 1,10-phenanthroline (phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10- phenanthroline (NO2 -phen). These Re(I) polymers, show marked differences in their photophysical properties when compared to single [pyRe(CO)3 (N^ N)]+ molecules in diluted solutions. For example, Re→phen charge transfer excited states (MLCT) in the Re(I) polymers undergo a more efficient annihilation and/or secondary photolysis than in [pyRe(CO)3 phen]+ complexes. Depending on solvent and/or cast film conditions, several aggregates of polymer strands with different morphologies were observed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques. Morphological changes derived from media-imposed changes (solvent, temperature) or from polymer backbone chemical modifications (protonation or peralkylation in P4VP uncoordinated pyridines) are responsible for the marked differences observed between the photophysical properties of these Re(I) polymers and those of the single pyRe(CO)3 (N^ N)+ molecules. Therefore, these Re(I) polymers can provide a good reaction scenario for other photochemical reactions. Thus, resonance energy transfer between –Re(CO)3 (tmphen)+ and –Re(CO)3 (NO2 -phen)+ pendants was observed in Re(I)-P4VP polymers containing both chromophores attached to their backbone. In addition, in the quenching of the MLCT luminescence of –Re(CO)3 (N^ N)+ pendants by amines, we observed a retardation of the molecular motion due to the restricted media that favored the observation of the Marcus inverted effect in bimolecular reactions due to the fact that low values of the solvent reorganization energies are achieved within aggregates.
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Poly-4-vinylpyridine polymers
Marcus inverted effect
Re(CO)3(N^N)+ pendants
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:11336/141125

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network_name_str CONICET Digital (CONICET)
spelling Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendantsWolcan, EzequielPoly-4-vinylpyridine polymersMarcus inverted effectRe(CO)3(N^N)+ pendantshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We review the morphological and the photophysical properties of several inorganic polymers that can be prepared from poly-4- vinylpyridine (P4VP). These polymers contain –Re(CO)3 (N^ N)+ pendants attached to their backbone with α-diimine ligands (N^ N) such as 2,2´-bipyridine (bpy), 1,10-phenanthroline (phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10- phenanthroline (NO2 -phen). These Re(I) polymers, show marked differences in their photophysical properties when compared to single [pyRe(CO)3 (N^ N)]+ molecules in diluted solutions. For example, Re→phen charge transfer excited states (MLCT) in the Re(I) polymers undergo a more efficient annihilation and/or secondary photolysis than in [pyRe(CO)3 phen]+ complexes. Depending on solvent and/or cast film conditions, several aggregates of polymer strands with different morphologies were observed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques. Morphological changes derived from media-imposed changes (solvent, temperature) or from polymer backbone chemical modifications (protonation or peralkylation in P4VP uncoordinated pyridines) are responsible for the marked differences observed between the photophysical properties of these Re(I) polymers and those of the single pyRe(CO)3 (N^ N)+ molecules. Therefore, these Re(I) polymers can provide a good reaction scenario for other photochemical reactions. Thus, resonance energy transfer between –Re(CO)3 (tmphen)+ and –Re(CO)3 (NO2 -phen)+ pendants was observed in Re(I)-P4VP polymers containing both chromophores attached to their backbone. In addition, in the quenching of the MLCT luminescence of –Re(CO)3 (N^ N)+ pendants by amines, we observed a retardation of the molecular motion due to the restricted media that favored the observation of the Marcus inverted effect in bimolecular reactions due to the fact that low values of the solvent reorganization energies are achieved within aggregates.Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaCentro de Estudios sobre Ciencia, Desarrollo y Educación Superior2020-03info: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/11336/141125Wolcan, Ezequiel; Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants; Centro de Estudios sobre Ciencia, Desarrollo y Educación Superior; Science Reviews - from the end of the world; 1; 2; 3-2020; 66-912683-9288CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.52712/sciencereviews.v1i2.9info:eu-repo/semantics/altIdentifier/url/http://scirevfew.net/index.php/sciencereviews/article/view/9info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:59:56Zoai:ri.conicet.gov.ar:11336/141125instacron: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:34982025-09-29 09:59:56.798CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
title Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
spellingShingle Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
Wolcan, Ezequiel
Poly-4-vinylpyridine polymers
Marcus inverted effect
Re(CO)3(N^N)+ pendants
title_short Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
title_full Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
title_fullStr Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
title_full_unstemmed Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
title_sort Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants
dc.creator.none.fl_str_mv Wolcan, Ezequiel
author Wolcan, Ezequiel
author_facet Wolcan, Ezequiel
author_role author
dc.subject.none.fl_str_mv Poly-4-vinylpyridine polymers
Marcus inverted effect
Re(CO)3(N^N)+ pendants
topic Poly-4-vinylpyridine polymers
Marcus inverted effect
Re(CO)3(N^N)+ pendants
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 review the morphological and the photophysical properties of several inorganic polymers that can be prepared from poly-4- vinylpyridine (P4VP). These polymers contain –Re(CO)3 (N^ N)+ pendants attached to their backbone with α-diimine ligands (N^ N) such as 2,2´-bipyridine (bpy), 1,10-phenanthroline (phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10- phenanthroline (NO2 -phen). These Re(I) polymers, show marked differences in their photophysical properties when compared to single [pyRe(CO)3 (N^ N)]+ molecules in diluted solutions. For example, Re→phen charge transfer excited states (MLCT) in the Re(I) polymers undergo a more efficient annihilation and/or secondary photolysis than in [pyRe(CO)3 phen]+ complexes. Depending on solvent and/or cast film conditions, several aggregates of polymer strands with different morphologies were observed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques. Morphological changes derived from media-imposed changes (solvent, temperature) or from polymer backbone chemical modifications (protonation or peralkylation in P4VP uncoordinated pyridines) are responsible for the marked differences observed between the photophysical properties of these Re(I) polymers and those of the single pyRe(CO)3 (N^ N)+ molecules. Therefore, these Re(I) polymers can provide a good reaction scenario for other photochemical reactions. Thus, resonance energy transfer between –Re(CO)3 (tmphen)+ and –Re(CO)3 (NO2 -phen)+ pendants was observed in Re(I)-P4VP polymers containing both chromophores attached to their backbone. In addition, in the quenching of the MLCT luminescence of –Re(CO)3 (N^ N)+ pendants by amines, we observed a retardation of the molecular motion due to the restricted media that favored the observation of the Marcus inverted effect in bimolecular reactions due to the fact that low values of the solvent reorganization energies are achieved within aggregates.
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description We review the morphological and the photophysical properties of several inorganic polymers that can be prepared from poly-4- vinylpyridine (P4VP). These polymers contain –Re(CO)3 (N^ N)+ pendants attached to their backbone with α-diimine ligands (N^ N) such as 2,2´-bipyridine (bpy), 1,10-phenanthroline (phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10- phenanthroline (NO2 -phen). These Re(I) polymers, show marked differences in their photophysical properties when compared to single [pyRe(CO)3 (N^ N)]+ molecules in diluted solutions. For example, Re→phen charge transfer excited states (MLCT) in the Re(I) polymers undergo a more efficient annihilation and/or secondary photolysis than in [pyRe(CO)3 phen]+ complexes. Depending on solvent and/or cast film conditions, several aggregates of polymer strands with different morphologies were observed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques. Morphological changes derived from media-imposed changes (solvent, temperature) or from polymer backbone chemical modifications (protonation or peralkylation in P4VP uncoordinated pyridines) are responsible for the marked differences observed between the photophysical properties of these Re(I) polymers and those of the single pyRe(CO)3 (N^ N)+ molecules. Therefore, these Re(I) polymers can provide a good reaction scenario for other photochemical reactions. Thus, resonance energy transfer between –Re(CO)3 (tmphen)+ and –Re(CO)3 (NO2 -phen)+ pendants was observed in Re(I)-P4VP polymers containing both chromophores attached to their backbone. In addition, in the quenching of the MLCT luminescence of –Re(CO)3 (N^ N)+ pendants by amines, we observed a retardation of the molecular motion due to the restricted media that favored the observation of the Marcus inverted effect in bimolecular reactions due to the fact that low values of the solvent reorganization energies are achieved within aggregates.
publishDate 2020
dc.date.none.fl_str_mv 2020-03
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/11336/141125
Wolcan, Ezequiel; Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants; Centro de Estudios sobre Ciencia, Desarrollo y Educación Superior; Science Reviews - from the end of the world; 1; 2; 3-2020; 66-91
2683-9288
CONICET Digital
CONICET
url http://hdl.handle.net/11336/141125
identifier_str_mv Wolcan, Ezequiel; Morphology-dependent photophysical properties of Poly-4-vinylpyridine polymers containing –Re(CO)3 (N^N)+ pendants; Centro de Estudios sobre Ciencia, Desarrollo y Educación Superior; Science Reviews - from the end of the world; 1; 2; 3-2020; 66-91
2683-9288
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.52712/sciencereviews.v1i2.9
info:eu-repo/semantics/altIdentifier/url/http://scirevfew.net/index.php/sciencereviews/article/view/9
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 Centro de Estudios sobre Ciencia, Desarrollo y Educación Superior
publisher.none.fl_str_mv Centro de Estudios sobre Ciencia, Desarrollo y Educación Superior
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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