Design and Control of Perylene Supramolecular Polymers through Imide Substitutions

The number and type of new supramolecular polymer (SMP) systems have increased rapidly in recent years. Some of the key challenges faced for these novel systems include gaining full control over the mode of self-assembly, the creation of novel architectures and exploring functionality. Here we provide a critical overview of approaches related to perylene-based SMPs and discuss progress to exert control over these potentially important SMPs through chemical modification of the imide substituents. Imide substitutions affect self-assembly behaviour orthogonally to the intrinsic optoelectronic properties of the perylene core, making for a valuable approach to tune SMP properties. Several recent approaches are therefore highlighted, with a focus on controlling 1) morphology, 2) H- or J- aggregation, and 3) mechanism of growth and degree of aggregation using thermodynamic and kinetic control. Areas of potential future exploration and application of these functional SMPs are also explored.