In Situ Photoisomerization of an Azobenzene‐Based Triple Helicate with a Prolonged Thermal Relaxation Time
Jiajia Zhu, Xiao‐Wen Sun, Xintong Yang, Shu‐Na Yu, Lin Liang, Ya‐Zhi Chen, Xiaoyan Zheng, Meng Yu, Li Yan, Juan Tang, Wei Zhao, Xiao‐Juan Yang, Biao Wu
Abstract
(A=anion) with azobenzene-spaced bis-bis(urea) ligands (L) have proven to undergo a rare in situ photoisomerization (without disassembly of the structure) rather than the typically known, stepwise "disassembly-isomerization-reassembly" process. This is enabled by the structural self-adaptability of the "aniono" assembly arising from multiple relatively weak and flexible hydrogen bonds between the phosphate anion and bis(urea) units. Notably, the Z→E thermal relaxation rate of the isomerized azobenzene unit is significantly decreased (up to 20-fold) for the triple helicates compared to the free ligands. Moreover, the binding of chiral guest cations inside the cavity of the Z-isomerized triple helicate can induce optically pure diastereomers, thus demonstrating a new strategy for making light-activated chiroptical materials.