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 af dette arbejde

Kemisk Institut

21 Citationer (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).

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry A
Vol/bind	120
Udgave nummer	49
Sider (fra-til)	9782-9793
Antal sider	12
ISSN	1089-5639
DOI	https://doi.org/10.1021/acs.jpca.6b09646
Status	Udgivet - 2016

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10.1021/acs.jpca.6b09646

Citationsformater

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

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, bind 120, nr. 49, s. 9782-9793. https://doi.org/10.1021/acs.jpca.6b09646

@article{ead677ac5cc14b678defac993555a82c,

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).",

author = "Hansen, {Mia Harring} and Jonas Elm and Olsen, {Stine Tetzschner} and Gejl, {Aske N{\o}rskov} and Storm, {Freja Eils{\o}} and Frandsen, {Benjamin Normann} and Skov, {Anders Bo} and Nielsen, {Mogens Br{\o}ndsted} and Kj{\ae}rgaard, {Henrik Grum} and Mikkelsen, {Kurt Valentin}",

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doi = "10.1021/acs.jpca.6b09646",

language = "English",

volume = "120",

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T2 - increasing the energy storage capacity

AU - Hansen, Mia Harring

AU - Elm, Jonas

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

PY - 2016

Y1 - 2016

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).

U2 - 10.1021/acs.jpca.6b09646

DO - 10.1021/acs.jpca.6b09646

M3 - Journal article

C2 - 27973809

AN - SCOPUS:85006250774

SN - 1089-5639

VL - 120

SP - 9782

EP - 9793

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 49

ER -

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

Abstract

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