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

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DOIResolve DOI: http://doi.org/10.1021/jp400616c
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TypeArticle
Journal titleJournal of Physical Chemistry A
ISSN1089-5639
Volume117
Issue16
Pages33403347; # of pages: 8
SubjectAb 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
AbstractDihydroazulenes 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.
Publication date
LanguageEnglish
AffiliationSecurity and Disruptive Technologies; National Research Council Canada
Peer reviewedYes
NPARC number21270506
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Record identifierbe6f4011-ba6f-4143-9067-fdd1cecbf18b
Record created2014-02-14
Record modified2016-05-09
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