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

Oliver Schalk; Søren Lindbæk Broman; Michael Åxman Petersen; Dmitry V.  Khakhulin; Rasmus Yding Brogaard; Mogens Brøndsted Nielsen; Andrey E. Boguslavskiy; Albert Stolow; Theis Ivan Sølling

doi:10.1021/jp400616c

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

Oliver Schalk, Søren Lindbæk Broman, Michael Åxman Petersen, Dmitry V. Khakhulin, Rasmus Yding Brogaard, Mogens Brøndsted Nielsen, Andrey E. Boguslavskiy, Albert Stolow, Theis Ivan Sølling

Department of Chemistry

33 Citations (Scopus)

Abstract

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=₂ 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.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	117
Issue number	16
Pages (from-to)	3340-3347
Number of pages	8
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp400616c
Publication status	Published - 25 Apr 2013

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10.1021/jp400616c

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Schalk, O., Broman, S. L., Petersen, M. Å., Khakhulin, D. V., Brogaard, R. Y., Nielsen, M. B., Boguslavskiy, A. E., Stolow, A., & Sølling, T. I. (2013). On the condensed phase ring-closure of vinylheptafulvalene and ring-opening of gaseous dihydroazulene. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 117(16), 3340-3347. https://doi.org/10.1021/jp400616c

On the condensed phase ring-closure of vinylheptafulvalene and ring-opening of gaseous dihydroazulene. / Schalk, Oliver; Broman, Søren Lindbæk; Petersen, Michael Åxman et al.
In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 117, No. 16, 25.04.2013, p. 3340-3347.

Research output: Contribution to journal › Journal article › Research › peer-review

Schalk, O, Broman, SL, Petersen, MÅ, Khakhulin, DV, Brogaard, RY, Nielsen, MB, Boguslavskiy, AE, Stolow, A & Sølling, TI 2013, 'On the condensed phase ring-closure of vinylheptafulvalene and ring-opening of gaseous dihydroazulene', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, vol. 117, no. 16, pp. 3340-3347. https://doi.org/10.1021/jp400616c

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title = "On the condensed phase ring-closure of vinylheptafulvalene and ring-opening of gaseous dihydroazulene",

abstract = "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=2 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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AU - Schalk, Oliver

AU - Broman, Søren Lindbæk

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AU - Khakhulin, Dmitry V.

AU - Brogaard, Rasmus Yding

AU - Nielsen, Mogens Brøndsted

AU - Boguslavskiy, Andrey E.

AU - Stolow, Albert

AU - Sølling, Theis Ivan

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N2 - 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=2 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.

AB - 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=2 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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JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

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ER -

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

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