Theoretical Investigation of Substituent Effects on the Dihydroazulene/Vinylheptafulvene Photoswitch: Increasing the Energy Storage Capacity

Mia Harring Hansen, Jonas Elm, Stine T. Olsen, Aske Nørskov Gejl, Freja E. Storm, Benjamin N. Frandsen, Anders B. Skov, Mogens Brøndsted Nielsen, Henrik G. Kjaergaard, Kurt V. Mikkelsen

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent dihydroazulene and vinylheptafulvene compounds. We wish to increase the energy storage capacity, that is, the energy difference between the dihydroazulene and vinylheptafulvene isomers, of the photoswitch by computational molecular design and have performed over 9000 electronic structure calculations using density functional theory. Based on these calculations, we obtain design rules for how to increase the energy storage capacity of the photoswitch. Furthermore, we have investigated how the activation energy for the thermally induced vinylheptafulvene to dihydroazulene conversion depends on the substitution pattern, and based on these results, we have outlined molecular design considerations for obtaining new desired target structures exhibiting long energy storage times. Selected candidate systems have also been investigated in terms of optical properties to elucidate how sensitive the absorption maxima are to the functionalizations.
Original languageEnglish
JournalJournal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume120
Issue number49
Pages (from-to)9782-9793
Number of pages12
ISSN1089-5639
DOIs
Publication statusPublished - 2016
Externally publishedYes

Cite this

Hansen, Mia Harring ; Elm, Jonas ; Olsen, Stine T. ; Gejl, Aske Nørskov ; Storm, Freja E. ; Frandsen, Benjamin N. ; Skov, Anders B. ; Nielsen, Mogens Brøndsted ; Kjaergaard, Henrik G. ; Mikkelsen, Kurt V. / Theoretical Investigation of Substituent Effects on the Dihydroazulene/Vinylheptafulvene Photoswitch: Increasing the Energy Storage Capacity. In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory. 2016 ; Vol. 120, No. 49. pp. 9782-9793.
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title = "Theoretical Investigation of Substituent Effects on the Dihydroazulene/Vinylheptafulvene Photoswitch: Increasing the Energy Storage Capacity",
abstract = "We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent dihydroazulene and vinylheptafulvene compounds. We wish to increase the energy storage capacity, that is, the energy difference between the dihydroazulene and vinylheptafulvene isomers, of the photoswitch by computational molecular design and have performed over 9000 electronic structure calculations using density functional theory. Based on these calculations, we obtain design rules for how to increase the energy storage capacity of the photoswitch. Furthermore, we have investigated how the activation energy for the thermally induced vinylheptafulvene to dihydroazulene conversion depends on the substitution pattern, and based on these results, we have outlined molecular design considerations for obtaining new desired target structures exhibiting long energy storage times. Selected candidate systems have also been investigated in terms of optical properties to elucidate how sensitive the absorption maxima are to the functionalizations.",
author = "Hansen, {Mia Harring} and Jonas Elm and Olsen, {Stine T.} and Gejl, {Aske N{\o}rskov} and Storm, {Freja E.} and Frandsen, {Benjamin N.} and Skov, {Anders B.} and Nielsen, {Mogens Br{\o}ndsted} and Kjaergaard, {Henrik G.} and Mikkelsen, {Kurt V.}",
year = "2016",
doi = "10.1021/acs.jpca.6b09646",
language = "English",
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pages = "9782--9793",
journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",
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number = "49",

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Theoretical Investigation of Substituent Effects on the Dihydroazulene/Vinylheptafulvene Photoswitch: Increasing the Energy Storage Capacity. / Hansen, Mia Harring; Elm, Jonas; Olsen, Stine T.; Gejl, Aske Nørskov; Storm, Freja E.; Frandsen, Benjamin N.; Skov, Anders B.; Nielsen, Mogens Brøndsted; Kjaergaard, Henrik G.; Mikkelsen, Kurt V.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 120, No. 49, 2016, p. 9782-9793.

Research output: Contribution to journalJournal articleResearchpeer-review

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T1 - Theoretical Investigation of Substituent Effects on the Dihydroazulene/Vinylheptafulvene Photoswitch: Increasing the Energy Storage Capacity

AU - Hansen, Mia Harring

AU - Elm, Jonas

AU - Olsen, Stine T.

AU - Gejl, Aske Nørskov

AU - Storm, Freja E.

AU - Frandsen, Benjamin N.

AU - Skov, Anders B.

AU - Nielsen, Mogens Brøndsted

AU - Kjaergaard, Henrik G.

AU - Mikkelsen, Kurt V.

PY - 2016

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N2 - We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent dihydroazulene and vinylheptafulvene compounds. We wish to increase the energy storage capacity, that is, the energy difference between the dihydroazulene and vinylheptafulvene isomers, of the photoswitch by computational molecular design and have performed over 9000 electronic structure calculations using density functional theory. Based on these calculations, we obtain design rules for how to increase the energy storage capacity of the photoswitch. Furthermore, we have investigated how the activation energy for the thermally induced vinylheptafulvene to dihydroazulene conversion depends on the substitution pattern, and based on these results, we have outlined molecular design considerations for obtaining new desired target structures exhibiting long energy storage times. Selected candidate systems have also been investigated in terms of optical properties to elucidate how sensitive the absorption maxima are to the functionalizations.

AB - We have investigated the effects of substituents on the properties of the dihydroazulene/vinylheptafulvene photoswitch. The focus is on the changes of the thermochemical properties by placing electron withdrawing and donating groups on the monocyano and dicyano structures of the parent dihydroazulene and vinylheptafulvene compounds. We wish to increase the energy storage capacity, that is, the energy difference between the dihydroazulene and vinylheptafulvene isomers, of the photoswitch by computational molecular design and have performed over 9000 electronic structure calculations using density functional theory. Based on these calculations, we obtain design rules for how to increase the energy storage capacity of the photoswitch. Furthermore, we have investigated how the activation energy for the thermally induced vinylheptafulvene to dihydroazulene conversion depends on the substitution pattern, and based on these results, we have outlined molecular design considerations for obtaining new desired target structures exhibiting long energy storage times. Selected candidate systems have also been investigated in terms of optical properties to elucidate how sensitive the absorption maxima are to the functionalizations.

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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

SN - 1089-5639

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