Induced Circular Dichroism of Isotactic Poly(2-vinylpyridine) with Diverse and Tunable "Sergeants-and-Soldiers" Type Chiral Amplification.

ABSTRACT

Facile and efficient construction of the helical structure with diverse and tunable chiral amplification from an achiral polymer is attractive but remains a challenge to develop multiple functional materials. We report herein a macromolecular acid-base complex of highly isotactic poly(2-vinylpyridine) (mmmm > 99%), (+)-camphorsulfonic acid, and dodecylbenzensulfonic acid. The asymmetric induction of the chiral additive through the ionic interactions between pyridinium pendants and acid ions drives the polymer backbone to twist in a preferred direction in CHCl3 and its mixture with CH3CN. The sign and intensity of induced circular dichroism rely on the base to acid ratio, the chiral acid content, and the solvent nature. By systematically tuning the solvent composition, four distinct types of "sergeants-and-soldiers" mode chiral amplification are achieved for the first time within a single system owing to the solvent dependent bias of chiral-chiral and chiral-achiral ion pairs.