J Am Chem Soc. 2025 Apr 2. doi: 10.1021/jacs.5c00968. Online ahead of print.
ABSTRACT
Visualizing the sliding dynamics of a topological network can provide critical insight into determining the design and properties of mechanically interlocked materials. Although several auxiliary techniques have been proposed to infer the microscopic motion of rotaxanes, employing intuitive and convenient methods to explore the microscopic dynamics of a mechanically interlocked polymer remains a significant challenge. Herein, this work introduces a mechanically interlocked network (MIN) into the patterned surfaces for visualizing and regulating the sliding process of [2]rotaxane units through the evolution of surface wrinkles. Upon the photodimerization of the anthracene-functionalized polymer chain, the surface wrinkle can be formed after thermal treatment and subsequent cooling to room temperature. Specifically, the cross-linked films exhibit visible changes in wrinkle topography through the disruption of host-guest recognition by alkaline stimuli. Moreover, by leveraging the unique mechanical properties of surface wrinkles, we prolonged and amplified the originally extremely transient and difficult-to-detect sliding motion of rotaxane units in terms of time scale. Through statistical analysis of the changes in wrinkle morphology, we were able to correspondingly deconstruct the three processes of the rotaxane sliding motion: (I) unrestricted rapid sliding following host-guest dissociation; (II) restricted sliding; and (III) termination of sliding. The novel approach we propose opens a new avenue for studying the microscopic molecular motion of mechanically interlocked materials, facilitating the advancement and application of mechanically interlocked structures. In addition to using macroscopic surface patterns to visualize and explore microscopic molecular motion, the motion of microscopic molecules can also be used to regulate macroscopic surface patterns.
PMID:40173364 | DOI:10.1021/jacs.5c00968
