Photoswitchable Topological Regulation of Covalent Macrocycles, Molecular Recognition, and Interlocked Structures

Macrocycles represent one important class of functional molecules, and dynamic macrocycles with the potential of cleavability, adaptability, and topological conversion are challenging. Herein we report photoswitchable allosteric and topological control of dynamic covalent macrocycles and further the use in guest binding and mechanically interlocked molecules. The manipulation of competing ring‐chain equilibria and bond formation/scission within reaction systems enabled light‐induced structural regulation over dithioacetal and thioacetal dynamic bonds, accordingly realizing bidirectional switching between crown ether‐like covalent macrocycles and their linear counterparts. The on‐demand photoswitchable topological transformation of macrocycles further allowed guest recognition/release exhibiting controllable binding affinity and selectivity. To showcase the capability light‐triggered assembly/disassembly of diverse mechanically interlocked structures, such as rotaxanes and catenanes, was achieved. The realization of photoswitchable topological conversion of covalent macrocycles, which has been rarely reported before, demonstrates the potential of light‐triggered reactivity control and structural reconfiguration for enhanced complexity and sophisticated function. The strategies and results should be appealing to endeavors in molecular recognition, dynamic assemblies, molecular machines, and intelligent materials.