Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes

Autores
Moore, Gary F.; Megiatto, Jackson D.; Hambourger, Michael; Gervaldo, Miguel Andres; Kodis, Gerdenis; Moore, Thomas A.; Gust, Devens; Moore, Ana L.
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report the photophysical and electrochemical properties of phenol-pyrrolidino[60]fullerenes 1 and 2, in which the phenol hydroxyl group is ortho and para to the pyrrolidino group, respectively, as well as those of a phenyl-pyrrolidino[60]fullerene model compound, 3. For the ortho analog 1, the presence of an intramolecular hydrogen bond is supported by 1H NMR and FTIR characterization. The redox potential of the phenoxyl radical-phenol couple in this architecture is 240 mV lower than that observed in the associated para compound 2. Further, the C60 excited-state lifetime of the hydrogen-bonded compound 1 in benzonitrile is 260 ps, while the corresponding lifetime for 2 is identical to that of the model compound 3 at 1.34 ns. Addition of excess organic acid to a benzonitrile solution of 1 gives rise to a new species, 4, with an excited-state lifetime of 1.40 ns. In nonpolar aprotic solvents such as toluene, all three compounds have a C60 excited-state lifetime of ∼1 ns. These results suggest that the presence of an intramolecular H-bond in 1 poises the potential of phenoxyl radical-phenol redox couple at a value that it is thermodynamically capable of reducing the photoexcited fullerene. This is not the case for the para analog 2 nor is it the case for the protonated species 4. This work illustrates that in addition to being used as light activated electron acceptors, pyrrolidino fullerenes are also capable of acting as built-in proton-accepting units that influence the potential of an attached donor when organized in an appropriate molecular design.
Fil: Moore, Gary F.. Lawrence Berkeley National Laboratory; Estados Unidos. Arizona State University; Estados Unidos
Fil: Megiatto, Jackson D.. Arizona State University; Estados Unidos
Fil: Hambourger, Michael. Arizona State University; Estados Unidos. Appalachian State University (appstate);
Fil: Gervaldo, Miguel Andres. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Kodis, Gerdenis. Arizona State University; Estados Unidos
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
Fil: Gust, Devens. Arizona State University; Estados Unidos
Fil: Moore, Ana L.. Arizona State University; Estados Unidos
Materia
Photosystem II
Fullerene
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:11336/199190
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/199190
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenesMoore, Gary F.Megiatto, Jackson D.Hambourger, MichaelGervaldo, Miguel AndresKodis, GerdenisMoore, Thomas A.Gust, DevensMoore, Ana L.Photosystem IIFullerenehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report the photophysical and electrochemical properties of phenol-pyrrolidino[60]fullerenes 1 and 2, in which the phenol hydroxyl group is ortho and para to the pyrrolidino group, respectively, as well as those of a phenyl-pyrrolidino[60]fullerene model compound, 3. For the ortho analog 1, the presence of an intramolecular hydrogen bond is supported by 1H NMR and FTIR characterization. The redox potential of the phenoxyl radical-phenol couple in this architecture is 240 mV lower than that observed in the associated para compound 2. Further, the C60 excited-state lifetime of the hydrogen-bonded compound 1 in benzonitrile is 260 ps, while the corresponding lifetime for 2 is identical to that of the model compound 3 at 1.34 ns. Addition of excess organic acid to a benzonitrile solution of 1 gives rise to a new species, 4, with an excited-state lifetime of 1.40 ns. In nonpolar aprotic solvents such as toluene, all three compounds have a C60 excited-state lifetime of ∼1 ns. These results suggest that the presence of an intramolecular H-bond in 1 poises the potential of phenoxyl radical-phenol redox couple at a value that it is thermodynamically capable of reducing the photoexcited fullerene. This is not the case for the para analog 2 nor is it the case for the protonated species 4. This work illustrates that in addition to being used as light activated electron acceptors, pyrrolidino fullerenes are also capable of acting as built-in proton-accepting units that influence the potential of an attached donor when organized in an appropriate molecular design.Fil: Moore, Gary F.. Lawrence Berkeley National Laboratory; Estados Unidos. Arizona State University; Estados UnidosFil: Megiatto, Jackson D.. Arizona State University; Estados UnidosFil: Hambourger, Michael. Arizona State University; Estados Unidos. Appalachian State University (appstate);Fil: Gervaldo, Miguel Andres. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Kodis, Gerdenis. Arizona State University; Estados UnidosFil: Moore, Thomas A.. Arizona State University; Estados UnidosFil: Gust, Devens. Arizona State University; Estados UnidosFil: Moore, Ana L.. Arizona State University; Estados UnidosRoyal Society of Chemistry2012-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/199190Moore, Gary F.; Megiatto, Jackson D.; Hambourger, Michael; Gervaldo, Miguel Andres; Kodis, Gerdenis; et al.; Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 11; 6; 6-2012; 1018-10251474-905X1474-9092CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi//10.1039/c2pp05351ainfo:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1039/c2pp05351a#citeasinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:54:16Zoai:ri.conicet.gov.ar:11336/199190instacron: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:34982025-10-15 14:54:17.165CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
title Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
spellingShingle Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
Moore, Gary F.
Photosystem II
Fullerene
title_short Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
title_full Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
title_fullStr Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
title_full_unstemmed Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
title_sort Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes
dc.creator.none.fl_str_mv Moore, Gary F.
Megiatto, Jackson D.
Hambourger, Michael
Gervaldo, Miguel Andres
Kodis, Gerdenis
Moore, Thomas A.
Gust, Devens
Moore, Ana L.
author Moore, Gary F.
author_facet Moore, Gary F.
Megiatto, Jackson D.
Hambourger, Michael
Gervaldo, Miguel Andres
Kodis, Gerdenis
Moore, Thomas A.
Gust, Devens
Moore, Ana L.
author_role author
author2 Megiatto, Jackson D.
Hambourger, Michael
Gervaldo, Miguel Andres
Kodis, Gerdenis
Moore, Thomas A.
Gust, Devens
Moore, Ana L.
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Photosystem II
Fullerene
topic Photosystem II
Fullerene
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 the photophysical and electrochemical properties of phenol-pyrrolidino[60]fullerenes 1 and 2, in which the phenol hydroxyl group is ortho and para to the pyrrolidino group, respectively, as well as those of a phenyl-pyrrolidino[60]fullerene model compound, 3. For the ortho analog 1, the presence of an intramolecular hydrogen bond is supported by 1H NMR and FTIR characterization. The redox potential of the phenoxyl radical-phenol couple in this architecture is 240 mV lower than that observed in the associated para compound 2. Further, the C60 excited-state lifetime of the hydrogen-bonded compound 1 in benzonitrile is 260 ps, while the corresponding lifetime for 2 is identical to that of the model compound 3 at 1.34 ns. Addition of excess organic acid to a benzonitrile solution of 1 gives rise to a new species, 4, with an excited-state lifetime of 1.40 ns. In nonpolar aprotic solvents such as toluene, all three compounds have a C60 excited-state lifetime of ∼1 ns. These results suggest that the presence of an intramolecular H-bond in 1 poises the potential of phenoxyl radical-phenol redox couple at a value that it is thermodynamically capable of reducing the photoexcited fullerene. This is not the case for the para analog 2 nor is it the case for the protonated species 4. This work illustrates that in addition to being used as light activated electron acceptors, pyrrolidino fullerenes are also capable of acting as built-in proton-accepting units that influence the potential of an attached donor when organized in an appropriate molecular design.
Fil: Moore, Gary F.. Lawrence Berkeley National Laboratory; Estados Unidos. Arizona State University; Estados Unidos
Fil: Megiatto, Jackson D.. Arizona State University; Estados Unidos
Fil: Hambourger, Michael. Arizona State University; Estados Unidos. Appalachian State University (appstate);
Fil: Gervaldo, Miguel Andres. Arizona State University; Estados Unidos. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Kodis, Gerdenis. Arizona State University; Estados Unidos
Fil: Moore, Thomas A.. Arizona State University; Estados Unidos
Fil: Gust, Devens. Arizona State University; Estados Unidos
Fil: Moore, Ana L.. Arizona State University; Estados Unidos
description We report the photophysical and electrochemical properties of phenol-pyrrolidino[60]fullerenes 1 and 2, in which the phenol hydroxyl group is ortho and para to the pyrrolidino group, respectively, as well as those of a phenyl-pyrrolidino[60]fullerene model compound, 3. For the ortho analog 1, the presence of an intramolecular hydrogen bond is supported by 1H NMR and FTIR characterization. The redox potential of the phenoxyl radical-phenol couple in this architecture is 240 mV lower than that observed in the associated para compound 2. Further, the C60 excited-state lifetime of the hydrogen-bonded compound 1 in benzonitrile is 260 ps, while the corresponding lifetime for 2 is identical to that of the model compound 3 at 1.34 ns. Addition of excess organic acid to a benzonitrile solution of 1 gives rise to a new species, 4, with an excited-state lifetime of 1.40 ns. In nonpolar aprotic solvents such as toluene, all three compounds have a C60 excited-state lifetime of ∼1 ns. These results suggest that the presence of an intramolecular H-bond in 1 poises the potential of phenoxyl radical-phenol redox couple at a value that it is thermodynamically capable of reducing the photoexcited fullerene. This is not the case for the para analog 2 nor is it the case for the protonated species 4. This work illustrates that in addition to being used as light activated electron acceptors, pyrrolidino fullerenes are also capable of acting as built-in proton-accepting units that influence the potential of an attached donor when organized in an appropriate molecular design.
publishDate 2012
dc.date.none.fl_str_mv 2012-06
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/11336/199190
Moore, Gary F.; Megiatto, Jackson D.; Hambourger, Michael; Gervaldo, Miguel Andres; Kodis, Gerdenis; et al.; Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 11; 6; 6-2012; 1018-1025
1474-905X
1474-9092
CONICET Digital
CONICET
url http://hdl.handle.net/11336/199190
identifier_str_mv Moore, Gary F.; Megiatto, Jackson D.; Hambourger, Michael; Gervaldo, Miguel Andres; Kodis, Gerdenis; et al.; Optical and electrochemical properties of hydrogen-bonded phenol-pyrrolidino[60]fullerenes; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 11; 6; 6-2012; 1018-1025
1474-905X
1474-9092
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi//10.1039/c2pp05351a
info:eu-repo/semantics/altIdentifier/url/https://link.springer.com/article/10.1039/c2pp05351a#citeas
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
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.22299

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