P/M Macromolecular Switch Based on Conformational Control Exerted by an Achiral Side Chain within an Axially Chiral Locked Pendant.

Molecular switches, supramolecular chemistry, and polymers can be combined to create stimuli-responsive multichiral materials. Therefore, by acting on the extended/bent conformational composition of an achiral arm, it is possible to create a macromolecular gear, where different supramolecular interactions can be activated/deactivated to control the helical sense of a polymer containing up to five different chiral axial motifs. For this, a chiral allene with a flexible achiral arm was introduced as a pendant in poly(phenylacetylene). Through flexible arm control between extended and bent conformations, it is possible to selectively induce either a P or M helical sense in the polymer, while the relative spatial distribution of the substituents in the allene remains unaltered in two perpendicular planes (configurationally locked). These results show that complex dynamic multichiral materials can be obtained by the polymerization of appropriate monomers that combine chirality, switching properties, and the ability to generate chiral supramolecular assemblies.