Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling

Detalhes bibliográficos
Autor(a) principal: Jesus, A. J. Lopes
Data de Publicação: 2020
Outros Autores: Reva, Igor, Nunes, Cláudio M., Roque, José P. L., Pinto, Sandra M. V., Lourenço, Rui Fausto
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10316/91155
https://doi.org/10.1016/j.cplett.2019.137069
Resumo: Monomers of 2-isocyanophenol were generated in low-temperature solid Ar and N2 matrices by UV-irradiation of benzoxazole and characterized by infrared (IR) spectroscopy. Near–IR narrowband excitation of the first OH-stretching overtone of 2–isocyanophenol isolated in an N2 matrix converted the most stable cis into the higher-energy trans conformer. Interconversions between these conformers also occurred when the sample was vibrationally excited by the full, or filtered, broadband light of the IR spectrometer source, notably, with different isomerization rate constants. A spontaneous trans → cis decay, via H–tunneling, was observed for N2 matrix kept in dark. In an Ar matrix, only the cis conformer was observed.
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spelling Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunnelingMatrix-isolation IR-spectroscopyConformational changesInfrared-induced chemistryIsomerization rate constantHydrogen atom tunnelingMonomers of 2-isocyanophenol were generated in low-temperature solid Ar and N2 matrices by UV-irradiation of benzoxazole and characterized by infrared (IR) spectroscopy. Near–IR narrowband excitation of the first OH-stretching overtone of 2–isocyanophenol isolated in an N2 matrix converted the most stable cis into the higher-energy trans conformer. Interconversions between these conformers also occurred when the sample was vibrationally excited by the full, or filtered, broadband light of the IR spectrometer source, notably, with different isomerization rate constants. A spontaneous trans → cis decay, via H–tunneling, was observed for N2 matrix kept in dark. In an Ar matrix, only the cis conformer was observed.Elsevier2020-05-16info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/91155http://hdl.handle.net/10316/91155https://doi.org/10.1016/j.cplett.2019.137069eng00092614https://www.sciencedirect.com/science/article/abs/pii/S0009261419310504Jesus, A. J. LopesReva, IgorNunes, Cláudio M.Roque, José P. L.Pinto, Sandra M. V.Lourenço, Rui Faustoinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2022-08-19T15:43:22Zoai:estudogeral.uc.pt:10316/91155Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:11:06.009716Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse
dc.title.none.fl_str_mv Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
title Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
spellingShingle Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
Jesus, A. J. Lopes
Matrix-isolation IR-spectroscopy
Conformational changes
Infrared-induced chemistry
Isomerization rate constant
Hydrogen atom tunneling
title_short Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
title_full Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
title_fullStr Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
title_full_unstemmed Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
title_sort Kinetically unstable 2–isocyanophenol isolated in cryogenic matrices: Vibrational excitation, conformational changes and spontaneous tunneling
author Jesus, A. J. Lopes
author_facet Jesus, A. J. Lopes
Reva, Igor
Nunes, Cláudio M.
Roque, José P. L.
Pinto, Sandra M. V.
Lourenço, Rui Fausto
author_role author
author2 Reva, Igor
Nunes, Cláudio M.
Roque, José P. L.
Pinto, Sandra M. V.
Lourenço, Rui Fausto
author2_role author
author
author
author
author
dc.contributor.author.fl_str_mv Jesus, A. J. Lopes
Reva, Igor
Nunes, Cláudio M.
Roque, José P. L.
Pinto, Sandra M. V.
Lourenço, Rui Fausto
dc.subject.por.fl_str_mv Matrix-isolation IR-spectroscopy
Conformational changes
Infrared-induced chemistry
Isomerization rate constant
Hydrogen atom tunneling
topic Matrix-isolation IR-spectroscopy
Conformational changes
Infrared-induced chemistry
Isomerization rate constant
Hydrogen atom tunneling
description Monomers of 2-isocyanophenol were generated in low-temperature solid Ar and N2 matrices by UV-irradiation of benzoxazole and characterized by infrared (IR) spectroscopy. Near–IR narrowband excitation of the first OH-stretching overtone of 2–isocyanophenol isolated in an N2 matrix converted the most stable cis into the higher-energy trans conformer. Interconversions between these conformers also occurred when the sample was vibrationally excited by the full, or filtered, broadband light of the IR spectrometer source, notably, with different isomerization rate constants. A spontaneous trans → cis decay, via H–tunneling, was observed for N2 matrix kept in dark. In an Ar matrix, only the cis conformer was observed.
publishDate 2020
dc.date.none.fl_str_mv 2020-05-16
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.uri.fl_str_mv http://hdl.handle.net/10316/91155
http://hdl.handle.net/10316/91155
https://doi.org/10.1016/j.cplett.2019.137069
url http://hdl.handle.net/10316/91155
https://doi.org/10.1016/j.cplett.2019.137069
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv 00092614
https://www.sciencedirect.com/science/article/abs/pii/S0009261419310504
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
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 Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
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instname_str Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
instacron_str RCAAP
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reponame_str Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
collection Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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