Ultra‐Tough, yet Rigid and Healable Supramolecular Polymers with Variable Stiffness for Multimodal Actuators

Variable stiffness materials have shown considerable application in soft robotics. However, previously reported materials often struggle to reconcile high stiffness, stretchability, toughness, and self‐healing ability, because of the inherently conflicting requisite of these properties in molecular design. Herein, we propose a novel strategy that involves incorporating acid‐base ionic pairs capable of from strong crosslinking sites into a dense and robust hydrogen‐bonding network to construct rigid self‐healing polymers with tunable stiffness and excellent toughness. To demonstrate these distinct features, the polymer was employed to serve as the strain‐regulation layers within a fiber‐reinforced pneumatic actuator (FPA). The exceptional synergy between the configuration versatility of FPA and the dynamic molecular behavior of the supramolecular polymers equips the actuator with simultaneous improvement in motion dexterity, multimodality, loading capacity, robustness, and durability. Additionally, the concept of integrating high dexterity at both macro‐ and micro‐scale is prospective to inspire the design of intelligent yet robust devices across various domains. Supramolecular polymers were developed by incorporating acid‐base ionic pairs into densely interconnected hydrogen networks, achieving both exceptional mechanical strength and dynamic chain flexibility. These materials can be utilized to create variable stiffness layers for soft actuators, enhancing their motion versatility and structural robustness.