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Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism
Multi-responsive functional molecules are key for obtaining user-defined control of the properties and functions of chemical and biological systems. In this respect, pH-responsive photochromes, whose switching can be directed with light and acid–base equilibria, have emerged as highly attractive mol...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179557/ https://www.ncbi.nlm.nih.gov/pubmed/34163724 http://dx.doi.org/10.1039/d0sc07000a |
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author | Medved', Miroslav Hoorens, Mark W. H. Di Donato, Mariangela Laurent, Adèle D. Fan, Jiayun Taddei, Maria Hilbers, Michiel Feringa, Ben L. Buma, Wybren Jan Szymanski, Wiktor |
author_facet | Medved', Miroslav Hoorens, Mark W. H. Di Donato, Mariangela Laurent, Adèle D. Fan, Jiayun Taddei, Maria Hilbers, Michiel Feringa, Ben L. Buma, Wybren Jan Szymanski, Wiktor |
author_sort | Medved', Miroslav |
collection | PubMed |
description | Multi-responsive functional molecules are key for obtaining user-defined control of the properties and functions of chemical and biological systems. In this respect, pH-responsive photochromes, whose switching can be directed with light and acid–base equilibria, have emerged as highly attractive molecular units. The challenge in their design comes from the need to accommodate application-defined boundary conditions for both light- and protonation-responsivity. Here we combine time-resolved spectroscopic studies, on time scales ranging from femtoseconds to seconds, with density functional theory (DFT) calculations to elucidate and apply the acidochromism of a recently designed iminothioindoxyl (ITI) photoswitch. We show that protonation of the thermally stable Z isomer leads to a strong batochromically-shifted absorption band, allowing for fast isomerization to the metastable E isomer with light in the 500–600 nm region. Theoretical studies of the reaction mechanism reveal the crucial role of the acid–base equilibrium which controls the populations of the protonated and neutral forms of the E isomer. Since the former is thermally stable, while the latter re-isomerizes on a millisecond time scale, we are able to modulate the half-life of ITIs over three orders of magnitude by shifting this equilibrium. Finally, stable bidirectional switching of protonated ITI with green and red light is demonstrated with a half-life in the range of tens of seconds. Altogether, we designed a new type of multi-responsive molecular switch in which protonation red-shifts the activation wavelength by over 100 nm and enables efficient tuning of the half-life in the millisecond–second range. |
format | Online Article Text |
id | pubmed-8179557 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81795572021-06-22 Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism Medved', Miroslav Hoorens, Mark W. H. Di Donato, Mariangela Laurent, Adèle D. Fan, Jiayun Taddei, Maria Hilbers, Michiel Feringa, Ben L. Buma, Wybren Jan Szymanski, Wiktor Chem Sci Chemistry Multi-responsive functional molecules are key for obtaining user-defined control of the properties and functions of chemical and biological systems. In this respect, pH-responsive photochromes, whose switching can be directed with light and acid–base equilibria, have emerged as highly attractive molecular units. The challenge in their design comes from the need to accommodate application-defined boundary conditions for both light- and protonation-responsivity. Here we combine time-resolved spectroscopic studies, on time scales ranging from femtoseconds to seconds, with density functional theory (DFT) calculations to elucidate and apply the acidochromism of a recently designed iminothioindoxyl (ITI) photoswitch. We show that protonation of the thermally stable Z isomer leads to a strong batochromically-shifted absorption band, allowing for fast isomerization to the metastable E isomer with light in the 500–600 nm region. Theoretical studies of the reaction mechanism reveal the crucial role of the acid–base equilibrium which controls the populations of the protonated and neutral forms of the E isomer. Since the former is thermally stable, while the latter re-isomerizes on a millisecond time scale, we are able to modulate the half-life of ITIs over three orders of magnitude by shifting this equilibrium. Finally, stable bidirectional switching of protonated ITI with green and red light is demonstrated with a half-life in the range of tens of seconds. Altogether, we designed a new type of multi-responsive molecular switch in which protonation red-shifts the activation wavelength by over 100 nm and enables efficient tuning of the half-life in the millisecond–second range. The Royal Society of Chemistry 2021-02-09 /pmc/articles/PMC8179557/ /pubmed/34163724 http://dx.doi.org/10.1039/d0sc07000a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Medved', Miroslav Hoorens, Mark W. H. Di Donato, Mariangela Laurent, Adèle D. Fan, Jiayun Taddei, Maria Hilbers, Michiel Feringa, Ben L. Buma, Wybren Jan Szymanski, Wiktor Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism |
title | Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism |
title_full | Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism |
title_fullStr | Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism |
title_full_unstemmed | Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism |
title_short | Tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism |
title_sort | tailoring the optical and dynamic properties of iminothioindoxyl photoswitches through acidochromism |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179557/ https://www.ncbi.nlm.nih.gov/pubmed/34163724 http://dx.doi.org/10.1039/d0sc07000a |
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