Pathway‐Dependent Self‐Assembly of Perylene Diimide/Peptide Conjugates in Aqueous Medium

Most molecular self‐assembly strategies involve equilibrium systems, leading to a single thermodynamic product as a result of weak, reversible non‐covalent interactions. Yet, strong non‐covalent interactions may result in non‐equilibrium self‐assembly, in which structural diversity is achieved by forming several kinetic products based on a single covalent building block. We demonstrate that well‐defined amphiphilic molecular systems based on perylene diimide/peptide conjugates exhibit kinetically controlled self‐assembly in aqueous medium, enabling pathway‐dependent assembly sequences, in which different organic nanostructures are evolved in a stepwise manner. The self‐assembly process was characterized using UV/Vis circular dichroism (CD) spectroscopy, and cryogenic transmission electron microscopy (cryo‐TEM). Our findings show that pathway‐controlled self‐assembly may significantly broaden the methodology of non‐covalent synthesis.