Cargando…
Mechanistic Elucidation of the Hula-Twist Photoreaction in Hemithioindigo
[Image: see text] The Hula-Twist (HT) photoreaction represents a fundamental photochemical pathway for bond isomerizations and is defined by the coupled motion of a double bond and an adjacent single bond. This photoreaction has been suggested as the defining motion for a plethora of light-responsiv...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10347542/ https://www.ncbi.nlm.nih.gov/pubmed/37364887 http://dx.doi.org/10.1021/jacs.3c03536 |
_version_ | 1785073570506866688 |
---|---|
author | Fischer, Tobias Leitner, Jonas Gerwien, Aaron Mayer, Peter Dreuw, Andreas Dube, Henry Wachtveitl, Josef |
author_facet | Fischer, Tobias Leitner, Jonas Gerwien, Aaron Mayer, Peter Dreuw, Andreas Dube, Henry Wachtveitl, Josef |
author_sort | Fischer, Tobias |
collection | PubMed |
description | [Image: see text] The Hula-Twist (HT) photoreaction represents a fundamental photochemical pathway for bond isomerizations and is defined by the coupled motion of a double bond and an adjacent single bond. This photoreaction has been suggested as the defining motion for a plethora of light-responsive chromophores such as retinal within opsins, coumaric acid within photoactive yellow protein, or vitamin D precursors, and stilbenes in solution. However, due to the fleeting character of HT photoproducts a direct experimental observation of this coupled molecular motion was severely hampered until recently. To solve this dilemma, the Dube group has designed a molecular framework able to deliver unambiguous experimental evidence of the HT photoreaction. Using sterically crowded atropisomeric hemithioindigo (HTI) the HT photoproducts are rendered thermally stable and can be observed directly after their formation. However, following the ultrafast excited state process of the HT photoreaction itself has not been achieved so far and thus crucial information for an elementary understanding is still missing. In this work, we present the first ultrafast spectroscopy study of the HT photoreaction in HTI and probe the competition between different excited state processes. Together with extensive excited state calculations a detailed mechanistic picture is developed explaining the significant solvent effects on the HT photoreaction and revealing the intricate interplay between productive isomerizations and unproductive twisted intramolecular charge transfer (TICT) processes. With this study essential insights are thus gained into the mechanism of complex multibond rotations in the excited state, which will be of primary importance for further developments in this field. |
format | Online Article Text |
id | pubmed-10347542 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-103475422023-07-15 Mechanistic Elucidation of the Hula-Twist Photoreaction in Hemithioindigo Fischer, Tobias Leitner, Jonas Gerwien, Aaron Mayer, Peter Dreuw, Andreas Dube, Henry Wachtveitl, Josef J Am Chem Soc [Image: see text] The Hula-Twist (HT) photoreaction represents a fundamental photochemical pathway for bond isomerizations and is defined by the coupled motion of a double bond and an adjacent single bond. This photoreaction has been suggested as the defining motion for a plethora of light-responsive chromophores such as retinal within opsins, coumaric acid within photoactive yellow protein, or vitamin D precursors, and stilbenes in solution. However, due to the fleeting character of HT photoproducts a direct experimental observation of this coupled molecular motion was severely hampered until recently. To solve this dilemma, the Dube group has designed a molecular framework able to deliver unambiguous experimental evidence of the HT photoreaction. Using sterically crowded atropisomeric hemithioindigo (HTI) the HT photoproducts are rendered thermally stable and can be observed directly after their formation. However, following the ultrafast excited state process of the HT photoreaction itself has not been achieved so far and thus crucial information for an elementary understanding is still missing. In this work, we present the first ultrafast spectroscopy study of the HT photoreaction in HTI and probe the competition between different excited state processes. Together with extensive excited state calculations a detailed mechanistic picture is developed explaining the significant solvent effects on the HT photoreaction and revealing the intricate interplay between productive isomerizations and unproductive twisted intramolecular charge transfer (TICT) processes. With this study essential insights are thus gained into the mechanism of complex multibond rotations in the excited state, which will be of primary importance for further developments in this field. American Chemical Society 2023-06-26 /pmc/articles/PMC10347542/ /pubmed/37364887 http://dx.doi.org/10.1021/jacs.3c03536 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Fischer, Tobias Leitner, Jonas Gerwien, Aaron Mayer, Peter Dreuw, Andreas Dube, Henry Wachtveitl, Josef Mechanistic Elucidation of the Hula-Twist Photoreaction in Hemithioindigo |
title | Mechanistic Elucidation
of the Hula-Twist Photoreaction
in Hemithioindigo |
title_full | Mechanistic Elucidation
of the Hula-Twist Photoreaction
in Hemithioindigo |
title_fullStr | Mechanistic Elucidation
of the Hula-Twist Photoreaction
in Hemithioindigo |
title_full_unstemmed | Mechanistic Elucidation
of the Hula-Twist Photoreaction
in Hemithioindigo |
title_short | Mechanistic Elucidation
of the Hula-Twist Photoreaction
in Hemithioindigo |
title_sort | mechanistic elucidation
of the hula-twist photoreaction
in hemithioindigo |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10347542/ https://www.ncbi.nlm.nih.gov/pubmed/37364887 http://dx.doi.org/10.1021/jacs.3c03536 |
work_keys_str_mv | AT fischertobias mechanisticelucidationofthehulatwistphotoreactioninhemithioindigo AT leitnerjonas mechanisticelucidationofthehulatwistphotoreactioninhemithioindigo AT gerwienaaron mechanisticelucidationofthehulatwistphotoreactioninhemithioindigo AT mayerpeter mechanisticelucidationofthehulatwistphotoreactioninhemithioindigo AT dreuwandreas mechanisticelucidationofthehulatwistphotoreactioninhemithioindigo AT dubehenry mechanisticelucidationofthehulatwistphotoreactioninhemithioindigo AT wachtveitljosef mechanisticelucidationofthehulatwistphotoreactioninhemithioindigo |