Catalytic One-Handed Helix Induction and Subsequent Static Memory of Poly(biphenylylacetylene)s Assisted by a Small Amount of Carboxy Groups Introduced at the Pendants

ACS Macro Lett. 2022 Apr 19;11(4):525-531. doi: 10.1021/acsmacrolett.2c00136. Epub 2022 Mar 28.

Abstract

A dynamically racemic helical copolymer composed of an achiral biphenylylacetylene (BPA) bearing methoxymethoxy groups at the 2,2'-positions and 1 mol % of an achiral BPA carrying 2-carboxy-2'-methoxymethoxy groups at the biphenyl pendants was found to fold into an excess one-handed helix with significant amplification of the helicity in the presence of a small amount of optically active amines. The induced macromolecular helicity was retained ("memorized") after removal of the chiral amines. The copolymer had a significant sensitivity for detecting the chirality of chiral amines with a sensitivity more than 10000-fold higher than that of the corresponding homopolymers with no carboxy group, thus showing Cotton effects even in the presence of a 0.01 equiv of an optically active amine. The effects of the substituents at the 4'-position of the biphenyl pendants of the copolymers and the structures of the chiral amines on the macromolecular helicity induction were also investigated.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amines* / chemistry
  • Catalysis
  • Macromolecular Substances
  • Polymers* / chemistry

Substances

  • Amines
  • Macromolecular Substances
  • Polymers