Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States

Abstract

By enchaining a small fraction of chiral monomer units, the helical sense of a dynamic polymer constructed from achiral monomer units can be disproportionately biased. This phenomenon, known as the sergeants-and-soldiers (S&S) effect, has been found to be widely applicable to dynamic covalent and supramolecular polymers. However, it has not been exemplified with a supramolecular polymer that features multiple helical states. Herein, we demonstrate the S&S effect in the context of the temperature-controlled supramolecular copolymerization of chiral and achiral biphenyl tetracarboxamides in alkanes. The one-dimensional helical structures presented in this study are unique because they exhibit three distinct helical states, two of which are triggered by coassembling with monomeric water that is codissolved in the solvent. The self-assembly pathways are rationalized using a combination of mathematical fitting and simulations with a thermodynamic mass-balance model. We observe an unprecedented case of an "abnormal"S&S effect by changing the side chains of the achiral soldier. Although the molecular structure of these aggregates remains elusive, the coassembly of water is found to have a profound impact on the helical excess.