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
Department of Chemistry, University of Copenhagen , Universitetsparken 5, 2100 Copenhagen Ø, Denmark.
Department of Physics, Helsinki University , P.O. Box 64, 00100 Helsinki, Finland.
J Phys Chem A. 2016 Dec 15;120(49):9782-9793. doi: 10.1021/acs.jpca.6b09646. Epub 2016 Dec 5.
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.
我们研究了取代基对二氢薁/乙烯基七富烯光开关性质的影响。重点在于通过在母体二氢薁和乙烯基七富烯化合物的单氰基和双氰基结构上引入吸电子基团和供电子基团，来研究热化学性质的变化。我们希望通过计算分子设计提高光开关的能量存储能力，即二氢薁和乙烯基七富烯异构体之间的能量差，并使用密度泛函理论进行了9000多次电子结构计算。基于这些计算，我们得出了如何提高光开关能量存储能力的设计规则。此外，我们研究了热诱导乙烯基七富烯向二氢薁转化的活化能如何依赖于取代模式，并基于这些结果，概述了获得具有长能量存储时间的新的所需目标结构的分子设计考量。还对选定的候选体系进行了光学性质研究，以阐明吸收最大值对官能化的敏感程度。
