TY - JOUR

T1 - Theoretical investigation of substituent effects on the dihydroazulene/vinylheptafulvene photoswitch

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

VL - 120

SP - 9782

EP - 9793

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

IS - 49

ER -