Angewandte Chemie, EarlyView.
The distinctive self‐assembling features of N‐annulated perylene bisimides 1 and 2 are reported. Diester 1 , with no H‐bonding interaction operating, affords stable cooperative J‐type supramolecular polymers. The incorporation of amide functional groups in 2 results in a stimulating differentiation with several pathways to achieve up to three J‐type aggregates and a fourth H‐type aggregate depending on the experimental conditions utilized. Key: methylcyclohexane (MCH), toluene (Tol).
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.