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Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization
The electrocyclic reaction dynamics of a photochromic dithiazolylarylene derivative, 2,3-dithiazolylbenzothiophene (DTA) was investigated by using time-resolved transient absorption and fluorescence spectroscopies. The closed-ring isomer of DTA undergoes cycloreversion through the conical intersecti...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9054205/ https://www.ncbi.nlm.nih.gov/pubmed/35520419 http://dx.doi.org/10.1039/d0ra03523h |
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author | Nagasaka, Tatsuhiro Sotome, Hikaru Morikawa, Soichiro Uriarte, Lucas Martinez Sliwa, Michel Kawai, Tsuyoshi Miyasaka, Hiroshi |
author_facet | Nagasaka, Tatsuhiro Sotome, Hikaru Morikawa, Soichiro Uriarte, Lucas Martinez Sliwa, Michel Kawai, Tsuyoshi Miyasaka, Hiroshi |
author_sort | Nagasaka, Tatsuhiro |
collection | PubMed |
description | The electrocyclic reaction dynamics of a photochromic dithiazolylarylene derivative, 2,3-dithiazolylbenzothiophene (DTA) was investigated by using time-resolved transient absorption and fluorescence spectroscopies. The closed-ring isomer of DTA undergoes cycloreversion through the conical intersection mediating the potential energy surfaces of the excited and ground states, which is in agreement with the Woodward–Hoffmann rules for the electrocyclic reactions of 6π electron systems. On the other hand, a large portion of the open-ring isomer undergoes cyclization along the distinct reaction scheme, in which the cyclization takes place in the excited state manifold leading to the formation of the excited state of the closed-ring isomer. The suppression of the geometrical motion of DTA due to the intramolecular interaction could open a new efficient reaction pathway resulting in the formation of the electronically excited state of the product. |
format | Online Article Text |
id | pubmed-9054205 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-90542052022-05-04 Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization Nagasaka, Tatsuhiro Sotome, Hikaru Morikawa, Soichiro Uriarte, Lucas Martinez Sliwa, Michel Kawai, Tsuyoshi Miyasaka, Hiroshi RSC Adv Chemistry The electrocyclic reaction dynamics of a photochromic dithiazolylarylene derivative, 2,3-dithiazolylbenzothiophene (DTA) was investigated by using time-resolved transient absorption and fluorescence spectroscopies. The closed-ring isomer of DTA undergoes cycloreversion through the conical intersection mediating the potential energy surfaces of the excited and ground states, which is in agreement with the Woodward–Hoffmann rules for the electrocyclic reactions of 6π electron systems. On the other hand, a large portion of the open-ring isomer undergoes cyclization along the distinct reaction scheme, in which the cyclization takes place in the excited state manifold leading to the formation of the excited state of the closed-ring isomer. The suppression of the geometrical motion of DTA due to the intramolecular interaction could open a new efficient reaction pathway resulting in the formation of the electronically excited state of the product. The Royal Society of Chemistry 2020-05-27 /pmc/articles/PMC9054205/ /pubmed/35520419 http://dx.doi.org/10.1039/d0ra03523h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Nagasaka, Tatsuhiro Sotome, Hikaru Morikawa, Soichiro Uriarte, Lucas Martinez Sliwa, Michel Kawai, Tsuyoshi Miyasaka, Hiroshi Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization |
title | Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization |
title_full | Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization |
title_fullStr | Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization |
title_full_unstemmed | Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization |
title_short | Restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization |
title_sort | restriction of the conrotatory motion in photo-induced 6π electrocyclic reaction: formation of the excited state of the closed-ring isomer in the cyclization |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9054205/ https://www.ncbi.nlm.nih.gov/pubmed/35520419 http://dx.doi.org/10.1039/d0ra03523h |
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