A Closed‐Loop Recyclable Hydrogel With Temperature‐Programmable Photomorphing Enabled by a Dynamic Spiropyran–Disulfide Network

The integration of programmable actuation with material circularity remains a critical challenge in the development of sustainable soft matter. Here, we report a dynamic covalent hydrogel that combines temperature‐programmable photomorphing with closed‐loop recyclability in a single material platform. The hydrogel is constructed from three dithiolane‐derived components, including a spiropyran‐modified thioctic acid (monomer ST), oligo(ethylene glycol)‐modified thioctic acid (OEG n ‐T), and a crosslinker (PEG‐T) containing two dithiolane end‐groups linked via a polyethylene glycol chain. Upon visible‐light irradiation, distinct macroscopic deformation modes, i.e., bending and then recovering or significant and fast bending without recovering, can be selectively programmed simply by adjusting the photoirradiation temperature. This temperature‐programmable photomorphing behaviour arises from the interplay between spiropyran photoisomerization and lower critical solution temperature (LCST)‐driven phase transition. The photomorphing function can be maintained after storage in aqueous solution or at dry ambient conditions for three weeks. Notably, the dynamic disulfide network enables efficient depolymerization under mild basic conditions, allowing recovery of up to 95% of the spiropyran‐modified monomer ST, establishing a closed‐loop lifecycle of monomer ST. These findings provide insights into the synergy effects of molecular isomerization and LCST‐driven phase transition within dynamic disulfide networks, offering a promising strategy toward next‐generation sustainable soft actuators with both sophisticated functionality and end‐of‐life circularity.