Hydrogelation Landscape Engineering and a Novel Strategy To Design Radically Induced Healable and Stimuli-Responsive Hydrogels.

Herein, we report the versatile ways to prepare both low-molecular weight hydrogels and polymeric hydrogels based on various types of supramolecular interactions, starting from a simple amphiphilic terpyridine-based molecule TPYA. Notably, we report that stable terpyridine-based radicals can be generated by light or heat irradiation in polymeric hydrogels based on hydrogen bonding interactions between -COOH of PAA and the terpyridine motif of TPYA for the first time. The generation of radicals is confirmed by EPR and UV-vis experiments, and the process is accompanied by significant color changes from white to dark purple. The stable radical hydrogels prepared by the supramolecular strategy are self-healing, stretchable, and self-supporting and can be molded into different geometrical shapes. It is deduced that the generation of terpyridine-based radicals enhances the intermolecular hydrogen bonding and π-π interaction of molecules in a hydrogel matrix, which is responsible for the self-healing ability. Finally, we also show that the radical gels can selectively respond to ammonia and stretch with reversible color changes based on the reversible hydrogen-bonding interaction.