Orthogonal Control of the Dynamics of Supramolecular Gels from Heterotelechelic Associating Polymers

One of the first examples of supramolecular gels presenting independent dual dynamics is built through a combination of hydrophobic and metal–ligand interactions. The associating building block consists in a water-soluble linear polymer terminated by a short hydrophobic sticker at one end, and a coordinating moiety at the other end. The distinct supramolecular nature of these noninterfering binding motifs allows the dynamics of the hydrogels to be finely tuned in an orthogonal fashion by the application of specific stimuli. Precisely, the solvent-induced plasticization of the hydrophobic associations and the acid-promoted dissociation of the metal–ligand complexes are used to control the network dynamics. By opposition to classically encountered binary gel–sol responses, we demonstrate that the stimuli-induced transition in material properties can be gradual, provided that the material structure is well designed and strong enough.