Highly Strong and Tough Supramolecular Polymer Networks Enabled by Cryptand‐Based Host−Guest Recognition

Supramolecular polymer networks (SPNs) demonstrate great potential in the development of smart materials owing to their attractive dynamic properties. However, suffering from the inherent weak bonding of most noncovalent cross-links, it remains a significant challenge to construct SPNs with outstanding mechanical performance. Herein, we exploit the cryptand/paraquat-guest recognition motifs as cross-links to prepare a class of highly strong and tough SPNs. Unlike those supramolecular cross-links with relatively weak binding abilities, the cryptand-based host-guest interactions have a high association constant and steady complexing structure, which effectively stabilizes the network and resists mechanical deformation under external force. Such favorable structural stability endows our SPNs with greatly enhanced mechanical performance, compared with the control-1 cross-linked by the weakly complexed crown ether/secondary ammonium salt motif (Tensile strength: 21.1± 0.5 vs 2.8 ± 0.1 MPa; Young's modulus: 102.6± 4.8 vs 2.1 ± 0.3 MPa; Toughness: 90.4± 2.0 vs 10.8 ± 0.6 MJ/m3). Moreover, our SPNs also retain abundant dynamic properties including good abilities in energy dissipation, reprocessability and stimuli-responsiveness. These findings provide novel insights into the preparation of SPNs with enhanced mechanical properties, and promote the development of high-performance intelligent supramolecular materials.