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

Kemisk Institut

33 Citationer (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.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Vol/bind	117
Udgave nummer	16
Sider (fra-til)	3340-3347
Antal sider	8
ISSN	1089-5639
DOI	https://doi.org/10.1021/jp400616c
Status	Udgivet - 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.

I: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Bind 117, Nr. 16, 25.04.2013, s. 3340-3347.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › 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, bind 117, nr. 16, s. 3340-3347. https://doi.org/10.1021/jp400616c

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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

AU - Petersen, Michael Åxman

AU - Khakhulin, Dmitry V.

AU - Brogaard, Rasmus Yding

AU - Nielsen, Mogens Brøndsted

AU - Boguslavskiy, Andrey E.

AU - Stolow, Albert

AU - Sølling, Theis Ivan

PY - 2013/4/25

Y1 - 2013/4/25

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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