A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione

Detalhes bibliográficos
Autor(a) principal: Lucas, Nanci Câmara de
Data de Publicação: 2009
Outros Autores: Elias, Mônica Maciel, Firme, Caio Lima, Corrêa, Rodrigo José, Garden, Simon John, Netto-Ferreira, José Carlos, Nicodem, David Ernest
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UFRN
Texto Completo: https://repositorio.ufrn.br/jspui/handle/123456789/29209
Resumo: The photochemical hydrogen abstraction reaction of pyrene-4,5-dione (3) has been investigated by laser flash photolysis. Excitation (λ = 355 nm) of a degassed solution of 3 in acetonitrile resulted in the formation of a detectable transient with absorption maxima at 380 and 470 nm. This transient decays with a lifetime of around 4.8 μs and is quenched by oxygen. This transient is most probably a triplet state of 3. Addition of hydrogen donors, such as 2-propanol; 1,4-cyclohexadiene or 4-methoxyphenol led to the formation of a new transient with λmax at 380, 500 nm and a broad absorption at 640 nm. This new transient slowly decays with second order kinetics and was assigned to the semiquinone radical obtained from the hydrogen abstraction reaction. Using DFT and AIM calculations the reactivity of 3 and 9,10-phenanthrenequinone (1) is best interpreted as a proton coupled electron transfer like mechanism for the hydrogen abstraction from 2-propanol.
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spelling Lucas, Nanci Câmara deElias, Mônica MacielFirme, Caio LimaCorrêa, Rodrigo JoséGarden, Simon JohnNetto-Ferreira, José CarlosNicodem, David Ernest2020-06-10T03:13:03Z2020-06-10T03:13:03Z2009-01-01LUCAS, Nanci Câmara de; ELIAS, Mônica Maciel; FIRME, Caio Lima; CORRÊA, Rodrigo José; GARDEN, Simon John; NETTO-FERREIRA, José Carlos; NICODEM, David Ernest. A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione. Journal Of Photochemistry And Photobiology A: Chemistry, [s. l.], v. 201, n. 1, p. 1-7, jan. 2009. ISSN 1010-6030. DOI https://doi.org/10.1016/j.jphotochem.2008.08.014. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S1010603008003791#!. Acesso em: 19 maio 2020.1010-6030https://repositorio.ufrn.br/jspui/handle/123456789/2920910.1016/j.jphotochem.2008.08.014ElsevierAttribution 3.0 Brazilhttp://creativecommons.org/licenses/by/3.0/br/info:eu-repo/semantics/openAccessLaser flash photolysisOrtho-quinoneTriplet excited stateDFTHydrogen atom transferA combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dioneinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleThe photochemical hydrogen abstraction reaction of pyrene-4,5-dione (3) has been investigated by laser flash photolysis. Excitation (λ = 355 nm) of a degassed solution of 3 in acetonitrile resulted in the formation of a detectable transient with absorption maxima at 380 and 470 nm. This transient decays with a lifetime of around 4.8 μs and is quenched by oxygen. This transient is most probably a triplet state of 3. Addition of hydrogen donors, such as 2-propanol; 1,4-cyclohexadiene or 4-methoxyphenol led to the formation of a new transient with λmax at 380, 500 nm and a broad absorption at 640 nm. This new transient slowly decays with second order kinetics and was assigned to the semiquinone radical obtained from the hydrogen abstraction reaction. Using DFT and AIM calculations the reactivity of 3 and 9,10-phenanthrenequinone (1) is best interpreted as a proton coupled electron transfer like mechanism for the hydrogen abstraction from 2-propanol.engreponame:Repositório Institucional da UFRNinstname:Universidade Federal do Rio Grande do Norte (UFRN)instacron:UFRNLICENSElicense.txtlicense.txttext/plain; charset=utf-81484https://repositorio.ufrn.br/bitstream/123456789/29209/3/license.txte9597aa2854d128fd968be5edc8a28d9MD53ORIGINALCombinedLaserFlashPhotolysis_Lucas_2009.pdfCombinedLaserFlashPhotolysis_Lucas_2009.pdfapplication/pdf577755https://repositorio.ufrn.br/bitstream/123456789/29209/1/CombinedLaserFlashPhotolysis_Lucas_2009.pdf52e660617370f01a858f23eb44c712f0MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8914https://repositorio.ufrn.br/bitstream/123456789/29209/2/license_rdf4d2950bda3d176f570a9f8b328dfbbefMD52TEXTCombinedLaserFlashPhotolysis_Lucas_2009.pdf.txtCombinedLaserFlashPhotolysis_Lucas_2009.pdf.txtExtracted texttext/plain37621https://repositorio.ufrn.br/bitstream/123456789/29209/4/CombinedLaserFlashPhotolysis_Lucas_2009.pdf.txt9eb42c1c27bd795fe5a5088cc09a7aa2MD54THUMBNAILCombinedLaserFlashPhotolysis_Lucas_2009.pdf.jpgCombinedLaserFlashPhotolysis_Lucas_2009.pdf.jpgGenerated Thumbnailimage/jpeg1691https://repositorio.ufrn.br/bitstream/123456789/29209/5/CombinedLaserFlashPhotolysis_Lucas_2009.pdf.jpg69a196c5fdf88a888db84a7a09624c5fMD55123456789/292092021-02-15 15:40:31.704oai:https://repositorio.ufrn.br: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Repositório de PublicaçõesPUBhttp://repositorio.ufrn.br/oai/opendoar:2021-02-15T18:40:31Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN)false
dc.title.pt_BR.fl_str_mv A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
spellingShingle A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
Lucas, Nanci Câmara de
Laser flash photolysis
Ortho-quinone
Triplet excited state
DFT
Hydrogen atom transfer
title_short A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_full A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_fullStr A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_full_unstemmed A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
title_sort A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
author Lucas, Nanci Câmara de
author_facet Lucas, Nanci Câmara de
Elias, Mônica Maciel
Firme, Caio Lima
Corrêa, Rodrigo José
Garden, Simon John
Netto-Ferreira, José Carlos
Nicodem, David Ernest
author_role author
author2 Elias, Mônica Maciel
Firme, Caio Lima
Corrêa, Rodrigo José
Garden, Simon John
Netto-Ferreira, José Carlos
Nicodem, David Ernest
author2_role author
author
author
author
author
author
dc.contributor.author.fl_str_mv Lucas, Nanci Câmara de
Elias, Mônica Maciel
Firme, Caio Lima
Corrêa, Rodrigo José
Garden, Simon John
Netto-Ferreira, José Carlos
Nicodem, David Ernest
dc.subject.por.fl_str_mv Laser flash photolysis
Ortho-quinone
Triplet excited state
DFT
Hydrogen atom transfer
topic Laser flash photolysis
Ortho-quinone
Triplet excited state
DFT
Hydrogen atom transfer
description The photochemical hydrogen abstraction reaction of pyrene-4,5-dione (3) has been investigated by laser flash photolysis. Excitation (λ = 355 nm) of a degassed solution of 3 in acetonitrile resulted in the formation of a detectable transient with absorption maxima at 380 and 470 nm. This transient decays with a lifetime of around 4.8 μs and is quenched by oxygen. This transient is most probably a triplet state of 3. Addition of hydrogen donors, such as 2-propanol; 1,4-cyclohexadiene or 4-methoxyphenol led to the formation of a new transient with λmax at 380, 500 nm and a broad absorption at 640 nm. This new transient slowly decays with second order kinetics and was assigned to the semiquinone radical obtained from the hydrogen abstraction reaction. Using DFT and AIM calculations the reactivity of 3 and 9,10-phenanthrenequinone (1) is best interpreted as a proton coupled electron transfer like mechanism for the hydrogen abstraction from 2-propanol.
publishDate 2009
dc.date.issued.fl_str_mv 2009-01-01
dc.date.accessioned.fl_str_mv 2020-06-10T03:13:03Z
dc.date.available.fl_str_mv 2020-06-10T03:13:03Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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status_str publishedVersion
dc.identifier.citation.fl_str_mv LUCAS, Nanci Câmara de; ELIAS, Mônica Maciel; FIRME, Caio Lima; CORRÊA, Rodrigo José; GARDEN, Simon John; NETTO-FERREIRA, José Carlos; NICODEM, David Ernest. A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione. Journal Of Photochemistry And Photobiology A: Chemistry, [s. l.], v. 201, n. 1, p. 1-7, jan. 2009. ISSN 1010-6030. DOI https://doi.org/10.1016/j.jphotochem.2008.08.014. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S1010603008003791#!. Acesso em: 19 maio 2020.
dc.identifier.uri.fl_str_mv https://repositorio.ufrn.br/jspui/handle/123456789/29209
dc.identifier.issn.none.fl_str_mv 1010-6030
dc.identifier.doi.none.fl_str_mv 10.1016/j.jphotochem.2008.08.014
identifier_str_mv LUCAS, Nanci Câmara de; ELIAS, Mônica Maciel; FIRME, Caio Lima; CORRÊA, Rodrigo José; GARDEN, Simon John; NETTO-FERREIRA, José Carlos; NICODEM, David Ernest. A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione. Journal Of Photochemistry And Photobiology A: Chemistry, [s. l.], v. 201, n. 1, p. 1-7, jan. 2009. ISSN 1010-6030. DOI https://doi.org/10.1016/j.jphotochem.2008.08.014. Disponível em: https://www.sciencedirect.com/science/article/abs/pii/S1010603008003791#!. Acesso em: 19 maio 2020.
1010-6030
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