On the Condensed Phase Ring-Closure of Vinylheptafulvalene and Ring-Opening of Gaseous Dihydroazulene

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-dihyd...

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Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-04, Vol.117 (16), p.3340-3347
Main Authors: Schalk, Oliver, Broman, Søren L, Petersen, Michael Å, Khakhulin, Dmitry V, Brogaard, Rasmus Y, Nielsen, Mogens Brøndsted, Boguslavskiy, Andrey E, Stolow, Albert, Sølling, Theis I
Format: Article
Language:English
Subjects:
Ab initio calculations
Atomic and molecular physics
Azulenes - chemistry
Bonding
Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations)
Condensing
Cyclopentanes - chemistry
Electronic structure of atoms, molecules and their ions: theory
Exact sciences and technology
Gas phases
Gases
Ground state
Isomerization
Kinetics
Light
Molecular Structure
Origins
Photoelectron Spectroscopy
Physical chemistry
Physics
Potential energy
Thermodynamics
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Summary: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.
ISSN:1089-5639
1520-5215
1520-5215
DOI:10.1021/jp400616c