Structural control can be achieved via the supramolecular polymerization of perylene diimides, where the morphology and function of aggregates is modulated by rational design of the perylene diimide monomers. Keywords: controllable self-assembly; functional materials; molecular design; perylene diimide; supramolecular polymers EN controllable self-assembly functional materials molecular design perylene diimide supramolecular polymers 1 1 1 01/18/22 20220113 NES 220113 B Aggregates of perylene b diimides are prized for their stability, efficiency and versatility in a range of optoelectronic applications.