N-Annulated Perylene Bisimides to Bias the Differentiation of Metastable Supramolecular Assemblies into J- and H-Aggregates

The unique self-assembling features of N-annulated perylene bisimides (PBIs) 1 and 2 are reported. The stability of the aggregates of diester 1 , in which no H-bonding interactions are operative, corroborates the significance of long-range van der Waals and dipole–dipole electrostatic interactions in the construction of stable supramolecular assemblies. The incorporation of amide functional groups within the N-annulated PBI in 2 stimulates pathway differentiation to achieve up to three J-type aggregates and a fourth H-type aggregate depending on the experimental conditions. The results presented demonstrate unprecedented levels of control over synthetic supramolecular self-assembly and the rich differentiation that N-annulated PBIs exhibit, opening the door to new, complex, functional supramolecular materials.