Transforming Commercial Polymers into Tough yet Switchable Adhesives by Trident Photoswitch Molecule Doping: Break Adhesion‐Switchability Paradox

Abstract Here, a trident molecule doping strategy is introduced to overcome both cohesion‐adhesion trade‐off and adhesion‐switchability conflict, transforming commercial polymers into tough yet photo‐switchable adhesives. The strategy involves initial rational design of new trident photoswitch molecules namely TAzo‐3 featuring azobenzene and hydroxy‐terminated alkyl chains involved rigid‐soft tri‐branch structure, and subsequent doping into commercial polycaprolactone (PCL) via simple blending. Unique design enables TAzo‐3 as a versatile dopant, not only regulating the internal and external supramolecular interaction to balance cohesion and interface adhesion for tough bonding, but also affording marked photothermal effect to facilitate rapid adhesive melting for great photo‐switchability. Thus, the optimal TAzo‐3‐doped PCL (TAzo‐3@P) displays markedly‐improved bonding performance on diverse substrates compared to linear azobenzene‐doped PCL and pure PCL. Impressively, TAzo‐3@P on polymethyl methacrylate (PMMA) attains large room‐temperature adhesion strength of 6.7 MPa – surpassing most reported adhesives and many commercial adhesives on PMMA, along with easy photo‐induced detachment with remarkable switch ratio of 2.09 × 10 5 . Besides, TAzo‐3@P can also act as “permanent” adhesives for only adhesion, demonstrating excellent multi‐reusability, anti‐freezing and waterproof ability. Mechanism studies unveil that the switchable adhesion is closely linked with the dopant molecule structure while rigid‐soft coupled trident structures and hydroxy‐terminated alkyl chains are key factors.