Impact of Metal Coordination on the Structures and Dynamics of Ethyl Acrylate‐Vinylimidazole Copolymers

The integration of weak sacrificial bonds into the polymer networks has become a universal approach for enhancing the mechanical properties of polymers. Particularly, the presence of non‐covalent associative interactions leads to significant changes in polymer dynamics and viscoelastic behaviors. In this study, we report a high‐performance metallo‐supramolecular elastomer based on metal‐imidazole coordination. Different metal ions, including Cu 2+ , Co 2+ , and Zn 2+ , were incorporated into a random copolymer composed of ethyl acrylate (EA) and 1‐vinylimidazole (VI), resulting in dramatic variation in mechanical and viscoelastic properties due to differences in metal‐coordination strength. High‐resolution 2D 1 H double‐quantum/single‐quantum (DQ/SQ) NMR spectroscopy directly reveals the formation of metal‐coordination in the polymer materials and shows that metal‐coordination leads to enhanced structural and dynamic heterogeneity. Specifically, both local segmental motions and terminal relaxation of metallo‐supramolecular elastomer are slowed down by the metal‐coordination. This study provides detailed molecular‐level insights into the structure and dynamics of polymer networks with varying metal‐coordination strengths, providing great potential for the rational design of high‐performance metallo‐supramolecular polymers.