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



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



Journal of Physical Chemistry. a 117(16): 3340-3347



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.

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Accession: 054735355

Download citation: RISBibTeXText

PMID: 23556480

DOI: 10.1021/jp400616c


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