Unexpectedly strong chiral amplification of chiral/achiral and chiral/chiral copolymers of biphenylylacetylenes and further enhancement/inversion and memory of the macromolecular helicity

We report an unexpectedly strong amplification of the macromolecular helicity in dynamic helical copolymers of chiral/achiral and chiral/chiral (R/S) biphenylylacetylenes in which the chiral residues are remote from the biphenyl pendants and further from the main chains. The copolymers consisting of 20 mol % chiral monomers and chiral monomers of 20% enantiomeric excess (ee) showed a full induced circular dichroism as intense as that of the chiral homopolymer. In contrast, an analogous poly(phenylacetylene) bearing the identical chiral residue (100% ee) showed no circular dichroism in the polymer backbone, indicating the critical role of the biphenyl moieties in the observed high chiral amplification. As anticipated, the helix-sense excesses of the copolymer backbones composed of a small amount of chiral units (<20 mol %) and chiral units of low ee (<20%) were reduced. Interestingly, however, the macromolecular helicity of the copolymers was further drastically enhanced as a greater excess of a one-handed helix or inverted upon noncovalent interaction with nonracemic alcohols and subsequently retained (memorized) after complete removal of the chiral alcohol. Even in a polymer consisting of completely racemic repeating units, one-handed right- and left-handed helices could almost be induced and memorized. These unique hierarchical amplifications and memory of the macromolecular helicity in the copolymers by the covalent and further noncovalent chiral interactions are quantitatively explained on the basis of a linear Ising model.