Effect of chirality in the supramolecular polymerization of N‐annulated perylenediimides: Cancelling pathway complexity

Abstract

Herein, the synthesis of two chiral NPBIs, (S)‐1 and (R)‐1, is reported and their self‐assembling features investigated. The reported NPBIs form chiral supramolecular polymers with a rich dichroic pattern by the π‐stacking of the aromatic backbones and the formation of an array of H‐bonds between the amide functional groups. Furthermore, the peripheral 3,4,5‐trialkoxy benzamide groups can form seven‐membered pseudocycles by the intramolecular H‐bonding interaction between the NH of the peripheral amides and one of the carbonyls of the imide units thus yielding a kinetically controlled self‐assembly process. Unlike achiral NPBI 1, that has been reported to form up to four supramolecular polymorphs, the reported chiral NPBIs form only a J‐type aggregated species. The results presented herein reveal how subtle changes exert an enormous influence on the supramolecular polymerization outcome.