A combined laser flash photolysis, density functional theory and atoms in molecules study of the photochemical hydrogen abstraction by pyrene-4,5-dione
Autor(a) principal: | |
---|---|
Data de Publicação: | 2009 |
Outros Autores: | , , , , , |
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. |
id |
UFRN_956dca5f40f1a8ad4f1821d039b3cda8 |
---|---|
oai_identifier_str |
oai:https://repositorio.ufrn.br:123456789/29209 |
network_acronym_str |
UFRN |
network_name_str |
Repositório Institucional da UFRN |
repository_id_str |
|
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 |
format |
article |
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 10.1016/j.jphotochem.2008.08.014 |
url |
https://repositorio.ufrn.br/jspui/handle/123456789/29209 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.rights.driver.fl_str_mv |
Attribution 3.0 Brazil http://creativecommons.org/licenses/by/3.0/br/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution 3.0 Brazil http://creativecommons.org/licenses/by/3.0/br/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional da UFRN instname:Universidade Federal do Rio Grande do Norte (UFRN) instacron:UFRN |
instname_str |
Universidade Federal do Rio Grande do Norte (UFRN) |
instacron_str |
UFRN |
institution |
UFRN |
reponame_str |
Repositório Institucional da UFRN |
collection |
Repositório Institucional da UFRN |
bitstream.url.fl_str_mv |
https://repositorio.ufrn.br/bitstream/123456789/29209/3/license.txt https://repositorio.ufrn.br/bitstream/123456789/29209/1/CombinedLaserFlashPhotolysis_Lucas_2009.pdf https://repositorio.ufrn.br/bitstream/123456789/29209/2/license_rdf https://repositorio.ufrn.br/bitstream/123456789/29209/4/CombinedLaserFlashPhotolysis_Lucas_2009.pdf.txt https://repositorio.ufrn.br/bitstream/123456789/29209/5/CombinedLaserFlashPhotolysis_Lucas_2009.pdf.jpg |
bitstream.checksum.fl_str_mv |
e9597aa2854d128fd968be5edc8a28d9 52e660617370f01a858f23eb44c712f0 4d2950bda3d176f570a9f8b328dfbbef 9eb42c1c27bd795fe5a5088cc09a7aa2 69a196c5fdf88a888db84a7a09624c5f |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Repositório Institucional da UFRN - Universidade Federal do Rio Grande do Norte (UFRN) |
repository.mail.fl_str_mv |
|
_version_ |
1814832674459615232 |