Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch: increasing the energy storage capacity

Mia Harring Hansen; Jonas Elm; Stine Tetzschner Olsen; Aske Nørskov Gejl; Freja Eilsø Storm; Benjamin Normann Frandsen; Anders Bo Skov; Mogens Brøndsted Nielsen; Henrik Grum Kjærgaard; Kurt Valentin Mikkelsen

doi:10.1021/acs.jpca.6b09646

Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch: increasing the energy storage capacity

Mia Harring Hansen, Jonas Elm, Stine Tetzschner Olsen, Aske Nørskov Gejl, Freja Eilsø Storm, Benjamin Normann Frandsen, Anders Bo Skov, Mogens Brøndsted Nielsen, Henrik Grum Kjærgaard, Kurt Valentin Mikkelsen^*

^*Corresponding author for this work

Department of Chemistry

21 Citations (Scopus)

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. (Figure Presented).

Original language	English
Journal	Journal of Physical Chemistry A
Volume	120
Issue number	49
Pages (from-to)	9782-9793
Number of pages	12
ISSN	1089-5639
DOIs	https://doi.org/10.1021/acs.jpca.6b09646
Publication status	Published - 2016

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Hansen, M. H., Elm, J., Olsen, S. T., Gejl, A. N., Storm, F. E., Frandsen, B. N., Skov, A. B., Nielsen, M. B., Kjærgaard, H. G., & Mikkelsen, K. V. (2016). Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch: increasing the energy storage capacity. Journal of Physical Chemistry A, 120(49), 9782-9793. https://doi.org/10.1021/acs.jpca.6b09646

Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch : increasing the energy storage capacity. / Hansen, Mia Harring; Elm, Jonas; Olsen, Stine Tetzschner et al.

In: Journal of Physical Chemistry A, Vol. 120, No. 49, 2016, p. 9782-9793.

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

Hansen, MH, Elm, J, Olsen, ST, Gejl, AN, Storm, FE, Frandsen, BN, Skov, AB, Nielsen, MB , Kjærgaard, HG & Mikkelsen, KV 2016, 'Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch: increasing the energy storage capacity', Journal of Physical Chemistry A, vol. 120, no. 49, pp. 9782-9793. https://doi.org/10.1021/acs.jpca.6b09646

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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. (Figure Presented).",

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AU - Olsen, Stine Tetzschner

AU - Gejl, Aske Nørskov

AU - Storm, Freja Eilsø

AU - Frandsen, Benjamin Normann

AU - Skov, Anders Bo

AU - Nielsen, Mogens Brøndsted

AU - Kjærgaard, Henrik Grum

AU - Mikkelsen, Kurt Valentin

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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. (Figure Presented).

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. (Figure Presented).

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ER -

Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch: increasing the energy storage capacity

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