Engineering Supramolecular Hydrogels via Reversible Photoswitching of Cucurbit[8]uril‐Spiropyran Complexation Stoichiometry

The integration of photoswitchable supramolecular units into hydrogels allows for spatiotemporal control over their nanoscale topological network and macroscale properties using light. Nevertheless, the current availability of photoswitchable supramolecular interactions for the development of such materials remains limited. Here, the molecular design of a novel photoswitchable cucurbit[8]uril-spiropyran host-guest complex exhibiting fast and reversible switching of binding ratios between 1:2 and 1:1 is reported. Photoswitchable complexation stoichiometries are rationally exploited as (de)crosslinking units in multiple polymers for the design of supramolecular hydrogels displaying highly dynamic and switchable features that are spatiotemporally controlled by light. The hydrogels exhibit rapid reversible mechanical softening-hardening upon alternating irradiation with blue and UV light, which is used to significantly accelerate and improve the efficiency of self-healing and shape-remolding of hydrogels. Furthermore, spiropyran endows such materials with unique reversible photochromic properties for reproducible patterning/erasing and information storage. Using a dual-light-assisted extrusion process, meter-scale hydrogel fibers with enhanced structural integrity and photoswitchable ionic conductivity are constructed and woven into various slidable knots and fluorescent shapes. This work represents an innovative molecular design strategy for advancing the development of spatiotemporally engineered supramolecular hydrogels using light and opens avenues for their prospective applications in dynamic materials and adaptive systems.