Hoorens Mark W H, Medved' Miroslav, Laurent Adèle D, Di Donato Mariangela, Fanetti Samuele, Slappendel Laura, Hilbers Michiel, Feringa Ben L, Jan Buma Wybren, Szymanski Wiktor
Department of Radiology, Medical Imaging Center, University Medical Center Groningen, University of Groningen, Hanzeplein 1, 9713 GZ, Groningen, The Netherlands.
Faculty of Science and Engineering, Centre for Systems Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 7, 9747 AG, Groningen, The Netherlands.
Nat Commun. 2019 Jun 3;10(1):2390. doi: 10.1038/s41467-019-10251-8.
Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical and biological systems, which is enabled through the use of molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation of absorption bands and are functional in various solvents including water, posing an unmet challenge. Here we show a class of fully-visible-light-operated molecular photoswitches, Iminothioindoxyls (ITIs) that meet these requirements. ITIs show a band separation of over 100 nm, isomerize on picosecond time scale and thermally relax on millisecond time scale. Using a combination of advanced spectroscopic and computational techniques, we provide the rationale for the switching behavior of ITIs and the influence of structural modifications and environment, including aqueous solution, on their photochemical properties. This research paves the way for the development of improved photo-controlled systems for a wide variety of applications that require fast responsive functions.
光对于精确控制化学和生物系统的性质与功能而言是一种特殊的外部刺激，这可通过使用分子光开关来实现。理想的光开关仅在可见光下运行，具有较大的吸收带间距，并且在包括水在内的各种溶剂中都能发挥作用，这构成了一项尚未解决的挑战。在此，我们展示了一类满足这些要求的全可见光操作分子光开关——亚氨基硫代吲哚（ITIs）。ITIs具有超过100纳米的带间距，在皮秒时间尺度上异构化，并在毫秒时间尺度上热弛豫。通过结合先进的光谱和计算技术，我们阐述了ITIs开关行为的原理以及结构修饰和环境（包括水溶液）对其光化学性质的影响。这项研究为开发用于各种需要快速响应功能的应用的改进型光控系统铺平了道路。
