Garcia-Amorós Jaume, Maerz Benjamin, Reig Marta, Cuadrado Alba, Blancafort Lluís, Samoylova Elena, Velasco Dolores
Grup de Materials Orgànics, Institut de Nanociència i Nanotecnologia (IN2UB), Departament de Química Inorgànica i Orgànica, (Secció de Química Orgànica), Universitat de Barcelona, Martí i Franquès 1, 08028, Barcelona, Spain.
Chair for BioMolecular Optics, Department of Physics, Ludwigs-Maximilians-University, Oettingenstrasse 67, 80538, Munich, Germany.
Chemistry. 2019 Jun 7;25(32):7726-7732. doi: 10.1002/chem.201900796. Epub 2019 May 9.
Azo dyes that combine electron-withdrawing thiazole/benzothiazole heterocycles and electron-donating amino groups within the very same covalent skeleton exhibit relaxation times for their thermal isomerization kinetics within milli- and microsecond timescales at room temperature. Notably, the thermal back reaction of the corresponding benzothiazolium and thiazolium salts occurred much faster, within the picosecond temporal domain. In fact, these new light-sensitive platforms are the first molecular azo derivatives capable of reversible switching between their trans and cis isomers in a subnanosecond timescale under ambient conditions. In addition, theoretical calculations revealed very low activation energies for the isomerization process, in accordance with the fast subnanosecond kinetics that were observed experimentally.
在同一共价骨架内结合吸电子噻唑/苯并噻唑杂环和供电子氨基的偶氮染料，在室温下其热异构化动力学的弛豫时间在毫秒和微秒时间尺度内。值得注意的是，相应的苯并噻唑鎓盐和噻唑鎓盐的热逆反应发生得更快，在皮秒时间域内。事实上，这些新型光敏感平台是首批能够在环境条件下在亚纳秒时间尺度内其反式和顺式异构体之间可逆切换的分子偶氮衍生物。此外，理论计算表明异构化过程的活化能非常低，这与实验观察到的快速亚纳秒动力学一致。
