Light‐Fueled Nonequilibrium and Adaptable Hydrogels for Highly Tunable Autonomous Self‐Oscillating Functions

Abstract Nonequilibrium oscillation fueled by dissipating chemical energy is ubiquitous in living systems for realizing a broad range of complex functions. The design of synthetic materials that can mimic their biological counterparts in the production of dissipative structures and autonomous oscillations is of great interest but remains challenging. Here, a series of environmentally adaptable hydrogels functionalized with photoswitchable spiropyran derivatives that display a tunable equilibrium‐shifting capability, thus endowing those hydrogels with a high degree of freedom and flexibility is reported. Such nonequilibrium hydrogels are able to responsively adapt their shapes under constant light illumination due to asymmetric deswelling, which in turn generates self‐shadowing and consequently creates autonomous self‐oscillating behaviors through a negative feedback process. Diverse oscillation modes including bending, twisting, and snap‐through buckling with tunable frequency and amplitude are widely observed in three different molecular systems. Density functional theory calculations and finite element simulations further demonstrated the robustness of such a photoadaptable self‐oscillation mechanism. This study provides a useful molecular design strategy for construction of highly adaptable hydrogels with potential applications in self‐sustained soft robots and autonomous devices.