Supramolecular hydrogels constructed through various host–guest interactions have attracted tremendous attention in view of their excellent dynamic and multi-stimuli responsive performances. Herein, benzyl (Bn) and azobenzene (Azo) grafted poly(ionic liquid)s (PILs) were prepared via a one-pot post-synthesis strategy. By virtue of the difference in binding affinity of Azo and Bn groups with the host compound cucurbituril [8] urea (CB[8]), the newly-developed supramolecular hydrogels exhibited distinctive photo- and thermo-responsive behaviors. Under UV light irradiation, PIL-Azo-Bn/CB[8] hydrogel got weaker, while a gel-to-sol transition was observed when treated by heating. Moreover, the above tunable behaviors were highly reversible. Variable-temperature measurements such as proton nuclear magnetic resonance and ultraviolet–visible spectroscopy illustrated that the photo- and thermo-regulated performances of PIL hydrogel were ascribed to the hierarchical host–guest interactions. As a prototype application in smart circuits, PIL hydrogel exhibited a photo- and thermo-tuned conductivity. Thus, our finding presented a novel and versatile platform to fabricate responsive functional hydrogels via host–guest interactions, which has great promising applications in smart materials and flexible sensors.
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