Pillar5arene‐Based Supramolecular Hydrogels with Tunable Mechanics and Multisubstrate Adhesion

Comprehensive Summary Adhesive hydrogels have shown great application potential in fields like biological medicine, catalyst, optical material, sensing, and analytical science. Up to now, cyclodextrin and cucurbituril are the most used macrocycles in adhesive hydrogels. However, CD/CB‐based adhesive hydrogel lacks multisubstrate adhesion to some extent. Although water‐soluble cationic pillararenes exhibit broad recognition capabilities toward diverse guest molecules and excellent water solubility and adhesiveness, their application in hydrogel field has rarely been reported due to the low synthetic yields and difficult purification of olefin‐functionalized derivatives. Herein, water‐soluble cationic pillar5arene (WP5) and guest molecules bearing olefin groups were combined via host‐guest interactions to form supramolecular monomer, which was utilized to construct pillararene‐based supramolecular hydrogels. The resulting hydrogel exhibited excellent mechanical properties with fracture elongation exceeding 1000%. Simultaneously, they demonstrated tunable self‐adhesive strength and displayed adhesion to diverse substrate materials. Leveraging this adhesion capability, modular hydrogel robots were constructed from the pillararene‐based supramolecular hydrogels, showing loading and transporting behaviors.