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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

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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… Click to show full 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.

Keywords: biphenylylacetylene; small amount; handed helix; one handed

Journal Title: ACS Macro Letters
Year Published: 2022

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