Photocontrolled Reversible Solid‐Fluid Transitions of Azopolymer Nanocomposites for Intelligent Nanomaterials

Abstract Intelligent polymer nanocomposites are multicomponent and multifunctional materials that show immense potential across diverse applications. However, to exhibit intelligent traits such as adaptability, reconfigurability and dynamic properties, these materials often require a solvent or heating environment to facilitate the mobility of polymer chains and nanoparticles, rendering their applications in everyday settings impractical. Here intelligent azopolymer nanocomposites that function effectively in a solvent‐free, room‐temperature environment based on photocontrolled reversible solid‐fluid transitions via switching flow temperatures (T_fs) are shown. A range of nanocomposites is synthesized through the grafting of Au nanoparticles, Au nanorods, quantum dots, or superparamagnetic nanoparticles with photoresponsive azopolymers. Leveraging the reversible cis‐trans photoisomerization of azo groups, the azopolymer nanocomposites transition between solid (T_f above room temperature) and fluid (T_f below room temperature) states. Such photocontrolled reversible solid‐fluid transitions empower the rewriting of nanopatterns, correction of nanoscale defects, reconfiguration of complex multiscale structures, and design of intelligent optical devices. These findings highlight T_f‐switchable polymer nanocomposites as promising candidates for the development of intelligent nanomaterials operative in solvent‐free, room‐temperature conditions.