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Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain

Azobenzene and its derivatives are one of the most widespread molecular scaffolds used in a range of modern applications, as well as in fundamental research. After photoexcitation, azo‐based photoswitches revert back to the most stable isomer on a timescale ([Formula: see text] ) that determines the...

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Autores principales: Vela, Sergi, Scheidegger, Alan, Fabregat, Raimon, Corminboeuf, Clémence
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7839710/
https://www.ncbi.nlm.nih.gov/pubmed/32991023
http://dx.doi.org/10.1002/chem.202003926
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author Vela, Sergi
Scheidegger, Alan
Fabregat, Raimon
Corminboeuf, Clémence
author_facet Vela, Sergi
Scheidegger, Alan
Fabregat, Raimon
Corminboeuf, Clémence
author_sort Vela, Sergi
collection PubMed
description Azobenzene and its derivatives are one of the most widespread molecular scaffolds used in a range of modern applications, as well as in fundamental research. After photoexcitation, azo‐based photoswitches revert back to the most stable isomer on a timescale ([Formula: see text] ) that determines the range of potential applications. Attempts to bring [Formula: see text] to extreme values prompted the development of azobenzene and azoheteroarene derivatives that either rebalance the E‐ and Z‐isomer stabilities, or exploit unconventional thermal isomerization mechanisms. In the former case, one successful strategy has been the creation of macrocycle strain, which tends to impact the E/Z stability asymmetrically, and thus significantly modify [Formula: see text] . On the bright side, bridged derivatives have shown an improved optical switching owing to the higher quantum yields and absence of degradation. However, in most (if not all) cases, bridged derivatives display a reversed thermal stability (more stable Z‐isomer), and smaller [Formula: see text] than the acyclic counterparts, which restricts their potential interest to applications requiring a fast forward and backwards switch. In this paper, the impact of alkyl bridges on the thermal stability of phenyl‐azoheteroarenes is investigated by using computational methods, and it is revealed that it is indeed possible to combine such improved photoswitching characteristics while preserving the regular thermal stability (more stable E‐isomer), and increased [Formula: see text] values under the appropriate connectivity and bridge length.
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spelling pubmed-78397102021-02-02 Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain Vela, Sergi Scheidegger, Alan Fabregat, Raimon Corminboeuf, Clémence Chemistry Full Papers Azobenzene and its derivatives are one of the most widespread molecular scaffolds used in a range of modern applications, as well as in fundamental research. After photoexcitation, azo‐based photoswitches revert back to the most stable isomer on a timescale ([Formula: see text] ) that determines the range of potential applications. Attempts to bring [Formula: see text] to extreme values prompted the development of azobenzene and azoheteroarene derivatives that either rebalance the E‐ and Z‐isomer stabilities, or exploit unconventional thermal isomerization mechanisms. In the former case, one successful strategy has been the creation of macrocycle strain, which tends to impact the E/Z stability asymmetrically, and thus significantly modify [Formula: see text] . On the bright side, bridged derivatives have shown an improved optical switching owing to the higher quantum yields and absence of degradation. However, in most (if not all) cases, bridged derivatives display a reversed thermal stability (more stable Z‐isomer), and smaller [Formula: see text] than the acyclic counterparts, which restricts their potential interest to applications requiring a fast forward and backwards switch. In this paper, the impact of alkyl bridges on the thermal stability of phenyl‐azoheteroarenes is investigated by using computational methods, and it is revealed that it is indeed possible to combine such improved photoswitching characteristics while preserving the regular thermal stability (more stable E‐isomer), and increased [Formula: see text] values under the appropriate connectivity and bridge length. John Wiley and Sons Inc. 2020-11-26 2021-01-04 /pmc/articles/PMC7839710/ /pubmed/32991023 http://dx.doi.org/10.1002/chem.202003926 Text en © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Full Papers
Vela, Sergi
Scheidegger, Alan
Fabregat, Raimon
Corminboeuf, Clémence
Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain
title Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain
title_full Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain
title_fullStr Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain
title_full_unstemmed Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain
title_short Tuning the Thermal Stability and Photoisomerization of Azoheteroarenes through Macrocycle Strain
title_sort tuning the thermal stability and photoisomerization of azoheteroarenes through macrocycle strain
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7839710/
https://www.ncbi.nlm.nih.gov/pubmed/32991023
http://dx.doi.org/10.1002/chem.202003926
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