Bridging Rigidity and Flexibility: Modulation of Supramolecular Hydrogels by Metal Complexation

The combination of complementary, noncovalent interactions is a key principle for the design of multistimuli responsive hydrogels. In this work, an amphiphilic peptide, supramacromolecular hydrogelator which combines metal-ligand coordination induced gelation and thermoresponsive toughening is reported. Following a modular approach, the incorporation of the triphenylalanine sequence FFF into a structural (C₃ ^EG ) and a terpyridine-functionalized (C₃ ^Tpy ) C₃ -symmetric monomer enables their statistical copolymerization into self-assembled, 1D nanorods in water, as investigated by circular dichroism (CD) spectroscopy and transmission electron microscopy (TEM). In the presence of a terpyridine functionalized telechelic polyethylene glycol (PEG) cross-linker, complex formation upon addition of different transition metal ions (Fe²⁺ , Zn²⁺ , Ni²⁺ ) induces the formation of soft, reversible hydrogels at a solid weight content of 1 wt% as observed by linear shear rheology. The viscoelastic behavior of Fe²⁺ and Zn²⁺ cross-linked hydrogels are basically identical, while the most kinetically inert Ni²⁺ coordinative bond leads to significantly weaker hydrogels, suggesting that the most dynamic rather than the most thermodynamically stable interaction supports the formation of robust and responsive hydrogel materials.