Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate
Autor(a) principal: | |
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Data de Publicação: | 2022 |
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/10316/101253 https://doi.org/10.1021/acs.jpca.2c01105 |
Resumo: | Photochromism of spiropyrans has attracted much attention due to its potential in many light-controlled system applications. However, several fundamental aspects regarding the structure, energetics, and mechanistic details of the transformations of spiropyrans are still not well understood. Here, we report the study of the photochromism of a 6-hydroxy-spiropyran (HBPS) under conditions of matrix isolation, where monomers of the compound are frozen in a solidified noble gas (krypton, at 15 K). The structure of the matrix-isolated HBPS was first elucidated by infrared (IR) spectroscopy supported by density functional theory computations. Then, the photochromism of HBPS, from the colorless spiropyran to the colored merocyanine, was induced by ultraviolet (UV) irradiation at 310 nm. The analysis of the IR spectrum of the photoproduced species revealed the exclusive formation of the most stable merocyanine MC-TTC stereoisomer. Subsequent visible-light (550 nm) irradiation of MC-TTC generated a new colorless allenic isomeric species ALN, where the UV irradiation (310 nm) of ALN was found to convert this species back to MC-TTC. This constitutes an unprecedented bidirectional transformation between a colored merocyanine and a colorless allene species. The newly observed photoswitching reaction (or photochromism) occurs along an intramolecular hydrogen bond existing in both merocyanine and allenic species, thus suggesting that it might be generally feasible in the chemistry of spiropyrans. On the other hand, the usual assumption that, as a general rule, merocyanines photochemically revert to spiropyrans is not supported in this work. |
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Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene IntermediatePhotochromism of spiropyrans has attracted much attention due to its potential in many light-controlled system applications. However, several fundamental aspects regarding the structure, energetics, and mechanistic details of the transformations of spiropyrans are still not well understood. Here, we report the study of the photochromism of a 6-hydroxy-spiropyran (HBPS) under conditions of matrix isolation, where monomers of the compound are frozen in a solidified noble gas (krypton, at 15 K). The structure of the matrix-isolated HBPS was first elucidated by infrared (IR) spectroscopy supported by density functional theory computations. Then, the photochromism of HBPS, from the colorless spiropyran to the colored merocyanine, was induced by ultraviolet (UV) irradiation at 310 nm. The analysis of the IR spectrum of the photoproduced species revealed the exclusive formation of the most stable merocyanine MC-TTC stereoisomer. Subsequent visible-light (550 nm) irradiation of MC-TTC generated a new colorless allenic isomeric species ALN, where the UV irradiation (310 nm) of ALN was found to convert this species back to MC-TTC. This constitutes an unprecedented bidirectional transformation between a colored merocyanine and a colorless allene species. The newly observed photoswitching reaction (or photochromism) occurs along an intramolecular hydrogen bond existing in both merocyanine and allenic species, thus suggesting that it might be generally feasible in the chemistry of spiropyrans. On the other hand, the usual assumption that, as a general rule, merocyanines photochemically revert to spiropyrans is not supported in this work.American Chemical Society2022-04-14info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/101253http://hdl.handle.net/10316/101253https://doi.org/10.1021/acs.jpca.2c01105eng1089-56391520-5215https://doi.org/10.1021/acs.jpca.2c01105Nunes, Cláudio MPereira, Nelson A MFausto, Ruiinfo: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:RCAAP2022-08-18T20:43:24Zoai:estudogeral.uc.pt:10316/101253Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:18:28.857418Repositório 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 |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate |
title |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate |
spellingShingle |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate Nunes, Cláudio M |
title_short |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate |
title_full |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate |
title_fullStr |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate |
title_full_unstemmed |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate |
title_sort |
Photochromism of a Spiropyran in Low-Temperature Matrices: Unprecedented Bidirectional Switching between a Merocyanine and an Allene Intermediate |
author |
Nunes, Cláudio M |
author_facet |
Nunes, Cláudio M Pereira, Nelson A M Fausto, Rui |
author_role |
author |
author2 |
Pereira, Nelson A M Fausto, Rui |
author2_role |
author author |
dc.contributor.author.fl_str_mv |
Nunes, Cláudio M Pereira, Nelson A M Fausto, Rui |
description |
Photochromism of spiropyrans has attracted much attention due to its potential in many light-controlled system applications. However, several fundamental aspects regarding the structure, energetics, and mechanistic details of the transformations of spiropyrans are still not well understood. Here, we report the study of the photochromism of a 6-hydroxy-spiropyran (HBPS) under conditions of matrix isolation, where monomers of the compound are frozen in a solidified noble gas (krypton, at 15 K). The structure of the matrix-isolated HBPS was first elucidated by infrared (IR) spectroscopy supported by density functional theory computations. Then, the photochromism of HBPS, from the colorless spiropyran to the colored merocyanine, was induced by ultraviolet (UV) irradiation at 310 nm. The analysis of the IR spectrum of the photoproduced species revealed the exclusive formation of the most stable merocyanine MC-TTC stereoisomer. Subsequent visible-light (550 nm) irradiation of MC-TTC generated a new colorless allenic isomeric species ALN, where the UV irradiation (310 nm) of ALN was found to convert this species back to MC-TTC. This constitutes an unprecedented bidirectional transformation between a colored merocyanine and a colorless allene species. The newly observed photoswitching reaction (or photochromism) occurs along an intramolecular hydrogen bond existing in both merocyanine and allenic species, thus suggesting that it might be generally feasible in the chemistry of spiropyrans. On the other hand, the usual assumption that, as a general rule, merocyanines photochemically revert to spiropyrans is not supported in this work. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-04-14 |
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/10316/101253 http://hdl.handle.net/10316/101253 https://doi.org/10.1021/acs.jpca.2c01105 |
url |
http://hdl.handle.net/10316/101253 https://doi.org/10.1021/acs.jpca.2c01105 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
1089-5639 1520-5215 https://doi.org/10.1021/acs.jpca.2c01105 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
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) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799134079172476928 |