Nishina Naoko, Mutai Toshiki, Aihara Jun-Ichi
Department of Chemistry, Faculty of Science, Shizuoka University , Oya, Shizuoka 422-8529, Japan.
Department of Materials and Environmental Science, Institute of Industrial Science, The University of Tokyo , Komaba, Meguro-ku, Tokyo 153-8505, Japan.
J Phys Chem A. 2017 Jan 12;121(1):151-161. doi: 10.1021/acs.jpca.6b11684. Epub 2016 Dec 21.
A general survey of excited-state intramolecular proton transfer (ESIPT) processes was made from the viewpoint of global aromaticity. For most ESIPT processes studied, a tautomeric product in the first excited electronic state was found to have a larger topological resonance energy (TRE) than the reactant in the same excited state. Conversely, if a transient tautomer is much less aromatic in the excited state than the reactant, an appreciable aromaticity-imposed energy barrier to the reaction will result. Thus, excited-state aromaticity is a very important factor, although not a definitive one, in determining the allowedness of ESIPT.
从全局芳香性的角度对激发态分子内质子转移（ESIPT）过程进行了全面综述。对于大多数所研究的ESIPT过程，发现处于第一激发电子态的互变异构产物比处于相同激发态的反应物具有更大的拓扑共振能（TRE）。相反，如果一个瞬态互变异构体在激发态下的芳香性比反应物小得多，那么反应将产生明显的由芳香性引起的能垒。因此，激发态芳香性是决定ESIPT反应能否发生的一个非常重要的因素，尽管不是唯一的决定性因素。
