On the condensed phase ring-closure of vinylheptafulvalene and ring-opening of gaseous dihydroazulene

Par Conseil national de recherches du Canada

DOI	Trouver le DOI : https://doi.org/10.1021/jp400616c
Auteur	Rechercher : Schalk, Oliver¹; Rechercher : Broman, Søren L.; Rechercher : Petersen, Michael Å.; Rechercher : Khakhulin, Dmitry V.; Rechercher : Brogaard, Rasmus Y.; Rechercher : Nielsen, Mogens Brøndsted; Rechercher : Boguslavskiy, Andrey E.¹; Rechercher : Stolow, Albert¹; Rechercher : Sølling, Theis I.
Affiliation	Conseil national de recherches du Canada. Technologies de sécurité et de rupture
Format	Texte, Article
Sujet	Ab initio computations; Biexponential decay; Cis-trans Isomerization; Condensed phase; Internal rotations; Ring opening reaction; Time-resolved photoelectron spectroscopy; Transient absorption; Photoelectron spectroscopy; cyclopentane derivative; dihydroazulene; X ray photoelectron spectroscopy; Azulenes; Cyclopentanes; Photoelectron Spectroscopy
Résumé	Dihydroazulenes are interesting because of their photoswitching behavior. While the ring-opening to vinylheptafulvalene (VHF) is light induced, the back reaction is known to proceed thermally. In the present paper, we show the first gas phase study of the ring-opening reaction of 2-phenyl-1,8a-dihydroazulene-1, 1-dicarbonitrile (Ph-DHA) by means of time-resolved photoelectron spectroscopy which permits us to follow the ring-opening process. Moreover, we investigated s-trans-Ph-VHF in a series of transient absorption experiments, supported by ab initio computations, to understand the origin of the absence of light-induced ring-closure. The transient absorption results show a biexponential decay governed by a hitherto unknown state. This state is accessed within 1-2 ps and return to the ground state is probably driven through a cis-trans isomerization about the exocyclic C1=C2 double bond. The rapid decrease in potential energy disfavors internal rotation to s-cis-Ph-VHF, the structure that would precede the ring-closure reaction.
Date de publication	2013-04-04
Dans	The Journal of Physical Chemistry A 117, nº 16 (4 avril 2013) : 3340–3347.
Langue	anglais
Publications évaluées par des pairs	Oui
Numéro NPARC	21270506
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Identificateur de l’enregistrement	be6f4011-ba6f-4143-9067-fdd1cecbf18b
Enregistrement créé	2014-02-14
Enregistrement modifié	2020-04-22

Date de modification :: 2024-07-17