Introducing a π-Skeleton Perpendicular to the Central Methylene Carbon in Alkanediamides: Design of Supramolecular Polymers with an Offset π-Stacking Arrangement

Abstract

The self-assembly behavior of a heptanediamide derivative that contains a four-ring fused π-skeleton on its central methylene carbon atom has been examined. This molecule, which also contains two octyl chains, gelated the nonpolar solvent methylcyclohexane through the formation of fibrous nanostructures with hydrogen-bonding networks through a cooperative nucleation–elongation process. The supramolecular polymerization is accompanied by bathochromic shifts of both the absorption and fluorescence bands while maintaining a fluorescence quantum yield comparable to that of the monomeric state. Theoretical calculations provided an energetically stable structure, in which the π-skeletons are stacked with an offset of more than 8.0 Å, replicating the experimentally observed absorption change due to exciton coupling. Moreover, a slow transition with an inversion of the chiral arrangement of the π-conjugated moieties was induced by replacing the octyl chains with chiral alkyl chains. Our molecular-design strategy was further applied to a five-ring fused π-skeleton, which also forms an offset π-stacking arrangement and exhibits more effective chiral exciton coupling in the aggregated state.