Macrocycle Exo‐Wall Complexation‐Mediated Supramolecular Slide‐Ring Networks

Slide‐ring polymers showed outstanding toughness and stretchability due to unique topological features through slide‐ring motion and spatial dynamic entanglement, yet their traditional covalent crosslinking structures limit their processability. Herein, we address this limitation by introducing a reversible supramolecular crosslinking strategy based on macrocycle exo‐wall complexation. Specifically, we report a supramolecular slide‐ring network constructed via orthogonal endo‐cavity and exo‐wall complexation of two naphthalene‐based macrocycles. The inner cavities of these macrocycles thread onto a polymer axle via host–guest inclusion with a 1,4‐diazabicyclo[2.2.2]octane derivative, while their electron‐rich external surface engages in charge‐transfer interactions with a naphthalene diimide guest, forming reversible noncovalent crosslinks. By integrating both binding modes into polyurethane networks, the resulting materials exhibit significantly enhanced breaking stress, stretchability, and toughness. Moreover, compared to the traditional slide‐ring polymer through covalent crosslinking, the dynamic and reversible nature of exo‐wall crosslinking endows the polymers with excellent processability, including spinning into high‐performance fibers with maintained mechanical performance. This work establishes a new paradigm for constructing processable slide‐ring polymers by replacing permanent covalent bonds with reversible noncovalent crosslinks.