Monomers Versus Prenucleation Clusters En Route to Polymorphism of Supramolecular Polymers

Abstract Polymorphism in supramolecular polymers is strongly correlated with the polymerization pathways underlying their formation. To effectively control emerging polymorphs, a comprehensive understanding of nucleation pathways and mechanisms is essential. Herein, a coronene‐dipeptide conjugate (Cr‐ o ‐FF OEt ) is introduced and its self‐assembly into two different stable 1D supramolecular polymorphs (Agg 1 and 2f) is observed in the same solvent composition (water/THF, 7:3 v/v) and same concentration at room temperature, following two competitive self‐assembly pathways. The difference in the mode of solvent addition triggers the two self‐assembly pathways. Furthermore, the isolated intermediate Agg 2i is found to transform into Agg 1 or Agg 2f under controlled experimental conditions. The supramolecular aggregates of Cr‐ o ‐FF OEt are thoroughly examined with the help of optical, chiroptical, and morphological techniques to understand the subtle difference in choosing the self‐assembling pathways. The studies reveal that the nanotube formation of Agg 1 follows a classical nucleation‐elongation supramolecular polymerization mechanism (involving monomers). In contrast, the helical fibers of Agg 2f are formed by the involvement of preorganized oligomers (nonclassical process). The observation highlights the underappreciated role of prenucleation clusters in pathway complexity and polymorphism of supramolecular 1D polymers.