Control of One-Handed Helicity in Polyacetylenes: Impact of an Extremely Small Amount of Chiral Substituents

  • Tsuyoshi Majima
    Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
  • Kosuke Oki
    Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
  • Nozomu Suzuki
    Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
  • Tomoyuki Ikai
    Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
  • Ryoma Ishidate
    Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
  • Shoki Takeda
    Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
  • Yuki Morita
    Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
  • Hiromi Aoi
    Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan
  • Katsuhiro Maeda
    Graduate School of Natural Science and Technology, Kanazawa University, Kanazawa 920-1192, Japan
  • Kento Okoshi
    Department of Applied Chemistry and Bioscience, Chitose Institute of Science and Technology, Chitose, Hokkaido 066-8655, Japan
  • Hajime Ohtani
    Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan
  • Eiji Yashima
    Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan

書誌事項

公開日
2023-11-06
資源種別
journal article
権利情報
  • https://creativecommons.org/licenses/by-nc-nd/4.0/
DOI
  • 10.1021/jacs.3c09308
公開者
American Chemical Society (ACS)

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説明

Controlling the one-handed helicity in synthetic polymers is crucial for developing helical polymer-based advanced chiral materials. We now report that an extremely small amount of chiral biphenylylacetylene (BPA) monomers (ca. 0.3-0.5 mol %) allows complete control of the one-handed helicity throughout the polymer chains mostly composed of achiral BPAs. Chiral substituents introduced at the 2-position of the biphenyl units of BPA positioned in the vicinity of the polymer backbones contribute to a significant amplification of the helical bias, as interpreted by theoretical modeling and simulation. The helical structures, such as the helical pitch and absolute helical handedness (right- or left-handed helix) of the one-handed helical copolymers, were unambiguously determined by high-resolution atomic force microscopy combined with X-ray diffraction. The exceptionally strong helix-biasing power of the chiral BPA provides a highly durable and practically useful chiral material for the separation of enantiomers in chromatography by copolymerization of an achiral functional BPA with a small amount of the chiral BPA (0.5 mol %) due to the robust helical scaffold of the one-handed helical copolymer.

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