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

Abstract

Abstract 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 2stimulates 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.