A New Class of Rigid Multi(azobenzene) Switches Featuring Electronic Decoupling: Unravelling the Isomerization in Individual Photochromes

Accès libre Peer reviewed | |
---|---|
Version acceptée pour publication (post-print auteur) | |
Paternité - Pas d'utilisation commerciale [CC] [BY] [NC] | |
Auteurs |
Agostino Galanti Jasmin Santoro Rajesh Mannancherry Quentin Duez Valentin Diez-Cabanes Michal Valášek Julien De Winter Jérôme Cornil Pascal Gerbaux Marcel Mayor Paolo Samorì |
Unité de recherche du site |
Institut de Science et d'Ingénierie Supramoléculaires - ISIS - UMR7006 |
Langue |
en |
Volume |
141 |
Numéro |
23 |
Page de début |
9273 |
Page de fin |
9283 |
Date de première publication |
2019-05-15 |
ISSN |
0002-7863 |
Titre de la source (revue, livre…) |
Journal of the American Chemical Society |
Résumé |
We report a novel class of star-shaped multiazobenzene photoswitches comprising individual photochromes connected to a central trisubstituted 1,3,5-benzene core. The unique design of such C3-symmetric molecules, consisting of conformationally rigid Show moreWe report a novel class of star-shaped multiazobenzene photoswitches comprising individual photochromes connected to a central trisubstituted 1,3,5-benzene core. The unique design of such C3-symmetric molecules, consisting of conformationally rigid and pseudoplanar scaffolds, made it possible to explore the role of electronic decoupling in the isomerization of the individual azobenzene units. The design of our tris-, bis-, and mono(azobenzene) compounds limits the π-conjugation between the switches belonging to the same molecule, thus enabling the efficient and independent isomerization of each photochrome. An in-depth experimental insight by making use of different complementary techniques such as UV–vis absorption spectroscopy, high performance liquid chromatography, and advanced mass spectrometry methods as ion mobility revealed an almost complete absence of electronic delocalization. Such evidence was further supported by both experimental (electrochemistry, kinetical analysis) and theoretical (DFT calculations) analyses. The electronic decoupling provided by this molecular design guarantees a remarkably efficient photoswitching of all azobenzenes, as evidenced by their photoisomerization quantum yields, as well as by the Z-rich UV photostationary states. Ion mobility mass spectrometry was exploited for the first time to study multiphotochromic compounds revealing the occurrence of a large molecular shape change in such rigid star-shaped azobenzene derivatives. In view of their high structural rigidity and efficient isomerization, our multiazobenzene photoswitches can be used as key components for the fabrication of complex stimuli-responsive porous materials. Show less |
DOI | 10.1021/jacs.9b02544 |
Titre abrégé de la source |
J. Am. Chem. Soc. |
Type de publication |
ACL |
Topic |
Chimie/Matériaux |
Unité de recherche extérieure au site |
Karlsruhe Institute of Technology KIT, Institute of Nanotechnology, P.O. Box3640, 76021 Karlsruhe, Germany |
Fonction |
aut |
Identifiant idREF |
109288335 |
Audience |
International |
Envoyer vers HAL |
5 |
URL | https://univoak.eu/islandora/object/islandora:79188 |