Self-healing metallo-supramolecular polymers from a ligand macromolecule synthesized via copper-catalyzed azide–alkyne cycloaddition and thiol–ene double “click” reactions

Abstract

In this study, we develop a series of new materials that can simultaneously and reversibly self-heal without external stimuli based on metallo-supramolecular interactions. Multiple tridentate 2,6-bis(1,2,3-trizaol-4-yl)pyridine (BTP) ligand units synthesized via a copper-catalyzed azide–alkyne cycloaddition (CuAAC) “click” reaction are incorporated into the polymer backbone of a ligand macromolecule through a thiol–ene “click” reaction. 3D transient supramolecular networks are formed from the ligand macromolecule upon coordination with transition and/or lanthanide metal ions. As compared to the ligand macromolecule, the resultant supramolecular films exhibit improved mechanical properties, such as Young's modulus, strength and toughness, which can be readily tuned by the stoichiometric ratio of Zn²⁺ to Eu³⁺ to Tb³⁺. The supramolecular films exhibit characteristics of weakly crosslinked networks where the storage modulus G′ and loss modulus G′′ scaled with normalized frequency ωa_T by the same slope of 0.5. Both the supramolecular bulk films and gels are found to exhibit fast and effective self-healing properties by virtue of the kinetically labile nature of the metal–ligand interactions.