Branched Oligomer‐Based Reversible Adhesives Enabled by Controllable Self‐Aggregation

Abstract Supramolecular adhesion material systems based on small molecules have shown great potential to unite the great contradiction between strong adhesion and reversibility. However, these material systems suffer from low adhesion strength/narrow adhesion span, limited designability, and single interaction due to fewer covalent bond content and action sites in small molecules. Herein, an ultrahigh‐strength and large‐span reversible adhesive enabled by a branched oligomer controllable self‐aggregation strategy is developed. The dense covalent bonds present in the branched oligomers greatly enhance adhesion strength without compromising reversibility. The resulting adhesive exhibits a large‐span reversible adhesion of ≈140 times, switching between ultra‐strong and tough adhesion strength (5.58 MPa and 5093.92 N m⁻¹) and ultralow adhesion (0.04 MPa and 87.656 N m⁻¹) with alternating temperature. Moreover, reversible dynamic double cross‐linking endows the adhesive with stable reversible adhesion transitions even after 100 cycles. This reversible adhesion property can also be remotely controlled via a voltage of 8 V, with a loading voltage duration of 45 s. This work paves the way for the design of reversible adhesives with long‐span outstanding properties using covalent polymers and offers a pathway for the rational design of high‐performance adhesives featuring both robust toughness and exceptional reversibility.