Institute for Organic and Analytical Chemistry, University of Bremen, Leobener Straße 7, 28359 Bremen, Germany.
MAPEX Center for Materials and Processes, University of Bremen, Bibliotheksstraße 1, 28359 Bremen, Germany.
J Org Chem. 2023 Mar 17;88(6):3372-3377. doi: 10.1021/acs.joc.2c00549. Epub 2022 Jun 30.
Azobenzene macrocycles (AzMs) represent a class of azobenzene that are typically photoswitchable with good switching yields of and isomers at certain photostationary states. Here, the synthesis and versatile functionalization of 12-membered AzMs is presented to obtain various - and -aryl-substituted AzMs in high yields of 71-98%. At different positions in the periphery, these substituents significantly impact on the thermal half-lives of the less-stable isomers. -substitution leads to faster thermal relaxation than -substitution, and electron-donating groups lead to a faster relaxation than electron-withdrawing groups.
偶氮苯大环（AzMs）是一类典型的光致变色化合物，在某些光稳定态下，其顺反异构的光致异构化产率可达 。本文介绍了 12 元偶氮苯大环的合成及其多功能化方法，以高产率（71-98%）得到了各种 - 和 - 芳基取代的偶氮苯大环。这些取代基在其外围的不同位置显著影响了不太稳定的 顺式异构体的热半衰期。- 取代比 - 取代导致更快的热弛豫，而给电子基团比吸电子基团导致更快的弛豫。
