Cooperative Supramolecular Polymerization Guided by Dispersive Interactions

Abstract Cooperative supramolecular polymerization is important for the synthesis of functional supramolecular homo and block‐copolymers of π‐systems. Current strategies indicate the need of strong hydrogen bonding (H‐bonding) and/or dipolar interactions in the π‐systems to achieve cooperativity. In sharp contrast, here we report the cooperative supramolecular polymerization in alkyl chain substituted perylene diimides (alkyl PDIs) driven by dispersive interactions with molecular level understanding. Moreover, alkyl PDIs follow cooperative mechanism with cooperativity similar to the strong H‐bonded π‐systems ( σ ∼10 −5 ) despite the lack of strong H‐bonding and dipolar interactions. Computer simulations show that this surprising phenomenon in alkyl PDIs is driven by the efficient dispersive interactions among the alkyl chains and π‐cores due to their zigzag arrangement in the supramolecular polymer. Importantly, alkyl PDIs display cooperative supramolecular polymerization in both polar and non‐polar solvents which is difficult for H‐bonded/dipolar π‐systems thus highlighting the advantages of dispersive interactions.