UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices
Autor(a) principal: | |
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Data de Publicação: | 2006 |
Outros Autores: | , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/5071 https://doi.org/10.1016/j.cplett.2006.08.061 |
Resumo: | Photochemical transformations of methyl coumalate have been studied by matrix-isolation technique. Two photoreactions were induced by UV ([lambda] > 295 nm) light: isomerisation to the Dewar form and [alpha]-bond cleavage leading to the open-ring aldehyde-ketene. The first photoprocess was found to be strongly dominating. Experimental evidence of photoreversibility of both photoisomerisation processes has been provided. Upon [lambda] > 200 nm irradiation, the photochemically formed monomeric Dewar species underwent decarboxylation, with production of methoxycarbonyl-substituted cyclobutadiene. This antiaromatic photoproduct was experimentally observed for the first time. All the photoproduced species were identified by comparison of their IR spectra with the spectra calculated at the DFT(B3LYP)/6-311++G(d,p) level. |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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7160 |
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UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matricesPhotochemical transformations of methyl coumalate have been studied by matrix-isolation technique. Two photoreactions were induced by UV ([lambda] > 295 nm) light: isomerisation to the Dewar form and [alpha]-bond cleavage leading to the open-ring aldehyde-ketene. The first photoprocess was found to be strongly dominating. Experimental evidence of photoreversibility of both photoisomerisation processes has been provided. Upon [lambda] > 200 nm irradiation, the photochemically formed monomeric Dewar species underwent decarboxylation, with production of methoxycarbonyl-substituted cyclobutadiene. This antiaromatic photoproduct was experimentally observed for the first time. All the photoproduced species were identified by comparison of their IR spectra with the spectra calculated at the DFT(B3LYP)/6-311++G(d,p) level.http://www.sciencedirect.com/science/article/B6TFN-4KNM6J9-C/1/0d0e18c865aa8f1c05481a9479a093292006info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleaplication/PDFhttp://hdl.handle.net/10316/5071http://hdl.handle.net/10316/5071https://doi.org/10.1016/j.cplett.2006.08.061engChemical Physics Letters. 429:4-6 (2006) 382-388Reva, I. D.Nowak, M. J.Lapinski, L.Fausto, R.info: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:RCAAP2021-10-04T10:42:31Zoai:estudogeral.uc.pt:10316/5071Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:31.304613Repositório 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 |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices |
title |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices |
spellingShingle |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices Reva, I. D. |
title_short |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices |
title_full |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices |
title_fullStr |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices |
title_full_unstemmed |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices |
title_sort |
UV-induced photochemistry of methyl coumalate (methyl 2-pyrone-5-carboxylate) isolated in low-temperature inert matrices |
author |
Reva, I. D. |
author_facet |
Reva, I. D. Nowak, M. J. Lapinski, L. Fausto, R. |
author_role |
author |
author2 |
Nowak, M. J. Lapinski, L. Fausto, R. |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Reva, I. D. Nowak, M. J. Lapinski, L. Fausto, R. |
description |
Photochemical transformations of methyl coumalate have been studied by matrix-isolation technique. Two photoreactions were induced by UV ([lambda] > 295 nm) light: isomerisation to the Dewar form and [alpha]-bond cleavage leading to the open-ring aldehyde-ketene. The first photoprocess was found to be strongly dominating. Experimental evidence of photoreversibility of both photoisomerisation processes has been provided. Upon [lambda] > 200 nm irradiation, the photochemically formed monomeric Dewar species underwent decarboxylation, with production of methoxycarbonyl-substituted cyclobutadiene. This antiaromatic photoproduct was experimentally observed for the first time. All the photoproduced species were identified by comparison of their IR spectra with the spectra calculated at the DFT(B3LYP)/6-311++G(d,p) level. |
publishDate |
2006 |
dc.date.none.fl_str_mv |
2006 |
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/10316/5071 http://hdl.handle.net/10316/5071 https://doi.org/10.1016/j.cplett.2006.08.061 |
url |
http://hdl.handle.net/10316/5071 https://doi.org/10.1016/j.cplett.2006.08.061 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Chemical Physics Letters. 429:4-6 (2006) 382-388 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
aplication/PDF |
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 instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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