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Direct evidence for hula twist and single-bond rotation photoproducts
Photoisomerization reactions are quintessential processes driving molecular machines and motors, govern smart materials, catalytic processes, and photopharmacology, and lie at the heart of vision, phototaxis, or vitamin production. Despite this plethora of applications fundamental photoisomerization...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2018
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6023863/ https://www.ncbi.nlm.nih.gov/pubmed/29955041 http://dx.doi.org/10.1038/s41467-018-04928-9 |
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author | Gerwien, Aaron Schildhauer, Monika Thumser, Stefan Mayer, Peter Dube, Henry |
author_facet | Gerwien, Aaron Schildhauer, Monika Thumser, Stefan Mayer, Peter Dube, Henry |
author_sort | Gerwien, Aaron |
collection | PubMed |
description | Photoisomerization reactions are quintessential processes driving molecular machines and motors, govern smart materials, catalytic processes, and photopharmacology, and lie at the heart of vision, phototaxis, or vitamin production. Despite this plethora of applications fundamental photoisomerization mechanisms are not well understood at present. The famous hula-twist motion—a coupled single and double-bond rotation—was proposed to explain proficient photoswitching in restricted environments but fast thermal follow-up reactions hamper identification of primary photo products. Herein we describe an asymmetric chromophore possessing four geometrically distinct diastereomeric states that do not interconvert thermally and can be crystallized separately. Employing this molecular setup direct and unequivocal evidence for the hula-twist photoreaction and for photoinduced single-bond rotation is obtained. The influences of the surrounding medium and temperature are quantified and used to favor unusual photoreactions. Based on our findings molecular engineers will be able to implement photo control of complex molecular motions more consciously. |
format | Online Article Text |
id | pubmed-6023863 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-60238632018-07-02 Direct evidence for hula twist and single-bond rotation photoproducts Gerwien, Aaron Schildhauer, Monika Thumser, Stefan Mayer, Peter Dube, Henry Nat Commun Article Photoisomerization reactions are quintessential processes driving molecular machines and motors, govern smart materials, catalytic processes, and photopharmacology, and lie at the heart of vision, phototaxis, or vitamin production. Despite this plethora of applications fundamental photoisomerization mechanisms are not well understood at present. The famous hula-twist motion—a coupled single and double-bond rotation—was proposed to explain proficient photoswitching in restricted environments but fast thermal follow-up reactions hamper identification of primary photo products. Herein we describe an asymmetric chromophore possessing four geometrically distinct diastereomeric states that do not interconvert thermally and can be crystallized separately. Employing this molecular setup direct and unequivocal evidence for the hula-twist photoreaction and for photoinduced single-bond rotation is obtained. The influences of the surrounding medium and temperature are quantified and used to favor unusual photoreactions. Based on our findings molecular engineers will be able to implement photo control of complex molecular motions more consciously. Nature Publishing Group UK 2018-06-28 /pmc/articles/PMC6023863/ /pubmed/29955041 http://dx.doi.org/10.1038/s41467-018-04928-9 Text en © The Author(s) 2018 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Gerwien, Aaron Schildhauer, Monika Thumser, Stefan Mayer, Peter Dube, Henry Direct evidence for hula twist and single-bond rotation photoproducts |
title | Direct evidence for hula twist and single-bond rotation photoproducts |
title_full | Direct evidence for hula twist and single-bond rotation photoproducts |
title_fullStr | Direct evidence for hula twist and single-bond rotation photoproducts |
title_full_unstemmed | Direct evidence for hula twist and single-bond rotation photoproducts |
title_short | Direct evidence for hula twist and single-bond rotation photoproducts |
title_sort | direct evidence for hula twist and single-bond rotation photoproducts |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6023863/ https://www.ncbi.nlm.nih.gov/pubmed/29955041 http://dx.doi.org/10.1038/s41467-018-04928-9 |
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