Supramolecular Polymerization of [5]Helicenes. Consequences of Self-Assembly on Configurational Stability

The supramolecular polymerization of [5]­helicenes <b>1</b> and <b>2</b> is investigated. The self-assembly of these helicenes proceeds by the operation of H-bonding interactions with a negligible participation of π-stacking. The enantiopurity of the sample has a dramatic effect on the supramolecular polymerization mechanism since it reverts the isodesmic mechanism for the racemic mixture to a cooperative one for the enantioenriched sample. Noticeably, the formation of supramolecular polymers efficiently increases the configurational stability of 1,14-unsubstituted [5]­helicenes.