Dynamic Regulation of Supramolecular Chirality in an Amphiphilic Dimeric Macrocycle Through Azobenzene‐Based Photoisomerization

ABSTRACT The dynamic control of supramolecular chirality continues to represent a significant challenge in the development of adaptive functional materials. Inspired by dynamic planar chirality modulation and the host‐guest chemistry of pillararenes, we report a stimuli‐responsive supramolecular system capable of reversible chirality switching within an amphiphilic dimeric macrocycle ( m ‐TPE WP5‐PCP ). This hybrid architecture, synthesized via meso ‐functionalization of pillar[5]arene and [1 5 ]paracyclophane, preserves orthogonal host‐guest properties while exhibiting unique amphiphilicity‐directed self‐assembly behavior. Under UV irradiation, trans ‐to‐ cis isomerization of an alanine‐substituted azobenzene guest induces stereoselective binding modes, which dynamically modulate the planar chirality and morphologies of m ‐TPE WP5‐PCP . Subsequent removal of the UV stimulus reverses the isomerization process, leading to the reformation of threaded complexes and the restoration of chiral supramolecular assemblies. This process demonstrates hierarchical regulation of supramolecular handedness via orthogonal molecular recognition pathways. The proposed strategy effectively integrates supramolecular chirality switching with stimuli‐responsive energy transduction, offering new avenues for the development of adaptive nanomaterials.