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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/141125
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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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1844613774677377024 |
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13.070432 |