Kinetic Delay in Cooperative Supramolecular Polymerization by Redefining the Trade‐Off Relationship between H‐Bonds and Van der Waals/π–π Stacking Interactions

We here present how rebalancing the interplay between H‐bonds and dispersive forces (Van der Waals/π–π stacking) may induce or not the generation of kinetic metastable states. In particular, we show that extending the aromatic content and favouring the interchain VdW interactions causes a delay into the cooperative supramolecular polymerization of a new family of toluene bis‐amide derivatives by trapping the metastable inactive state. Proper molecular engineering can open new opportunities to create kinetically metastable states in monomers undergoing cooperative supramolecular polymerizations. This occurs by favoring dispersive interactions over H‐bonds and thereby rebalancing the interplay between π–π stacking, Van der Waals, and hydrogen‐bonding interactions.