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)3phen]+ 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.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Materia
Química
poly-4-vinylpyridine polymers
–Re(CO)3(N^N)+ pendants
Marcus inverted effect
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/114771

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network_name_str SEDICI (UNLP)
spelling Morphology-dependent Photophysical Properties of Poly-4-vinylpyridine Polymers Containing–Re(CO)3(N^N)+ PendantsWolcan, EzequielQuímicapoly-4-vinylpyridine polymers–Re(CO)3(N^N)+ pendantsMarcus inverted effectWe 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)3phen]+ 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.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas2020-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf66-91http://sedici.unlp.edu.ar/handle/10915/114771enginfo:eu-repo/semantics/altIdentifier/url/http://www.scirevfew.net/index.php/sciencereviews/article/view/9info:eu-repo/semantics/altIdentifier/issn/2683-9288info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-29T11:26:44Zoai:sedici.unlp.edu.ar:10915/114771Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:26:44.789SEDICI (UNLP) - Universidad Nacional de La Platafalse
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
Química
poly-4-vinylpyridine polymers
–Re(CO)3(N^N)+ pendants
Marcus inverted effect
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 Química
poly-4-vinylpyridine polymers
–Re(CO)3(N^N)+ pendants
Marcus inverted effect
topic Química
poly-4-vinylpyridine polymers
–Re(CO)3(N^N)+ pendants
Marcus inverted effect
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)3phen]+ 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.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
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)3phen]+ 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
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dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/114771
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dc.language.none.fl_str_mv eng
language eng
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info:eu-repo/semantics/altIdentifier/issn/2683-9288
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
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