<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions

Photochromic molecules are systems that undergo a photoisomerization to high-energy isomers and are attractive for the storage of solar energy in a closed-energy cycle, for example, in molecular solar thermal energy storage systems. One challenge is to control the discharge time of the high-energy i...

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Autores principales:	Anna Ranzenigo, Franca M. Cordero, Martina Cacciarini, Mogens Brøndsted Nielsen
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	cross-conjugation electrocyclic reactions linear conjugation photochromism positional isomerism Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/2c886fd031e6409fa028df9d3ce7b30d
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spelling	oai:doaj.org-article:2c886fd031e6409fa028df9d3ce7b30d2021-11-11T18:28:16Z<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions10.3390/molecules262164621420-3049https://doaj.org/article/2c886fd031e6409fa028df9d3ce7b30d2021-10-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6462https://doaj.org/toc/1420-3049Photochromic molecules are systems that undergo a photoisomerization to high-energy isomers and are attractive for the storage of solar energy in a closed-energy cycle, for example, in molecular solar thermal energy storage systems. One challenge is to control the discharge time of the high-energy isomer. Here, we show that different substituents in the <i>ortho</i> position of a phenyl ring at C-2 of dihydroazulene (DHA-Ph) significantly increase the half-life of the metastable vinylheptafulvene (VHF-Ph) photoisomer; thus, the energy-releasing VHF-to-DHA back-reaction rises from minutes to days in comparison to the corresponding <i>para</i>- and <i>meta</i>-substituted systems. Systems with two photochromic DHA-Ph units connected by a diacetylene bridge either at the <i>para</i>, <i>meta</i> and <i>ortho</i> positions and corresponding to a linear or to a cross-conjugated pathway between the two photochromes are also presented. Here, the <i>ortho</i> substitution was found to compromise the switching properties. Thus, irradiation of <i>ortho</i>-bridged DHA-DHA resulted in degradation, probably due to the proximity of the different functional groups that can give rise to side-reactions.Anna RanzenigoFranca M. CorderoMartina CacciariniMogens Brøndsted NielsenMDPI AGarticlecross-conjugationelectrocyclic reactionslinear conjugationphotochromismpositional isomerismOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6462, p 6462 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	cross-conjugation electrocyclic reactions linear conjugation photochromism positional isomerism Organic chemistry QD241-441
spellingShingle	cross-conjugation electrocyclic reactions linear conjugation photochromism positional isomerism Organic chemistry QD241-441 Anna Ranzenigo Franca M. Cordero Martina Cacciarini Mogens Brøndsted Nielsen <i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions
description	Photochromic molecules are systems that undergo a photoisomerization to high-energy isomers and are attractive for the storage of solar energy in a closed-energy cycle, for example, in molecular solar thermal energy storage systems. One challenge is to control the discharge time of the high-energy isomer. Here, we show that different substituents in the <i>ortho</i> position of a phenyl ring at C-2 of dihydroazulene (DHA-Ph) significantly increase the half-life of the metastable vinylheptafulvene (VHF-Ph) photoisomer; thus, the energy-releasing VHF-to-DHA back-reaction rises from minutes to days in comparison to the corresponding <i>para</i>- and <i>meta</i>-substituted systems. Systems with two photochromic DHA-Ph units connected by a diacetylene bridge either at the <i>para</i>, <i>meta</i> and <i>ortho</i> positions and corresponding to a linear or to a cross-conjugated pathway between the two photochromes are also presented. Here, the <i>ortho</i> substitution was found to compromise the switching properties. Thus, irradiation of <i>ortho</i>-bridged DHA-DHA resulted in degradation, probably due to the proximity of the different functional groups that can give rise to side-reactions.
format	article
author	Anna Ranzenigo Franca M. Cordero Martina Cacciarini Mogens Brøndsted Nielsen
author_facet	Anna Ranzenigo Franca M. Cordero Martina Cacciarini Mogens Brøndsted Nielsen
author_sort	Anna Ranzenigo
title	<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions
title_short	<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions
title_full	<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions
title_fullStr	<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions
title_full_unstemmed	<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions
title_sort	<i>ortho</i>-substituted 2-phenyldihydroazulene photoswitches: enhancing the lifetime of the photoisomer by <i>ortho</i>-aryl interactions
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/2c886fd031e6409fa028df9d3ce7b30d
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<i>ortho</i>-Substituted 2-Phenyldihydroazulene Photoswitches: Enhancing the Lifetime of the Photoisomer by <i>ortho</i>-Aryl Interactions

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