Kinetic Evolution in Metal‐Dependent Self‐Assembly of Peptide–Terpyridine Conjugates

Abstract
Nature realizes impressive structures and emergent functions through precisely organized non‐covalent interactions, and this inspires the use of supramolecular motifs to engineer new materials. Herein, an amphiphilic peptide–terpyridine conjugate is reported that forms 1D nanostructures leading to hydrogels. Upon the addition of metal, a slow kinetic transition occurs, resulting in nanostructures which are dictated by the chosen metal binding to the terpyridine ligand. As such, bis‐complex formation between terminal terpyridines redirects the assembly from peptide‐driven 1D structures to an assortment of new nanostructures which evolve and appear over the course of weeks. Studies where pre‐existing peptide structures are disrupted prior to metal addition yield these same structures right away, further confirming the kinetically labored pathway to their formation when beginning from an assembled state.