Recent Progress in Azobenzene‐Based Supramolecular Materials and Applications

Abstract Azobenzene‐containing small molecules and polymers are functional photoswitchable molecules to form supramolecular nanomaterials for various applications. Recently, supramolecular nanomaterials have received enormous attention in material science because of their simple bottom‐up synthesis approach, understandable mechanisms and structural features, and batch‐to‐batch reproducibility. Azobenzene is a light‐responsive functional moiety in the molecular design of small molecules and polymers and is used to switch the photophysical properties of supramolecular nanomaterials. Herein, we review the latest literature on supramolecular nano‐ and micro‐materials formed from azobenzene‐containing small molecules and polymers through the combinatorial effect of weak molecular interactions. Different classes including complex coacervates, host‐guest systems, co‐assembled, and self‐assembled supramolecular materials, where azobenzene is an essential moiety in small molecules, and photophysical properties are discussed. Afterward, azobenzene‐containing polymers‐based supramolecular photoresponsive materials formed through the host‐guest approach, polymerization‐induced self‐assembly, and post‐polymerization assembly techniques are highlighted. In addition to this, the applications of photoswitchable supramolecular materials in pH sensing, and CO 2 capture are presented. In the end, the conclusion and future perspective of azobenzene‐based supramolecular materials for molecular assembly design, and applications are given.