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Synthesis of boron-containing buckybowl

Research Project

Project/Area Number 19K22184
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionKyoto University

Principal Investigator

Hiroto Satoru  京都大学, 人間・環境学研究科, 准教授 (30547427)

Project Period (FY) 2019-06-28 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2020: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Fiscal Year 2019: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Keywordsアザバッキーボウル / 曲面π共役分子 / ホウ素 / バッキーボウル / アルキン / n型半導体 / ボロン / 歪曲
Outline of Research at the Start

本研究ではホウ素元素を含む曲面分子の合成を目指す。ホウ素元素は電子受容性やフッ素との親和性を示し、分子に組み込むことで優れた電子材料の創出に繋がる。曲面構造をもつ分子に組み込むことで、電子受容性を示す新たな炭素材料の創出が期待できる。さらに、電極や発光材料への応用が期待されるホウ素ドープ型の炭素材料におけるホウ素の役割の解明に繋がり、性能の更なる向上の手がかりになると期待できる。まずは、ホウ素元素を分子の骨格に組み込む手法を開発し、その上で分子を歪め、目的のホウ素含有曲面分子の合成を目指す。

Outline of Final Research Achievements

π-conjugated molecules usually have a planar structure. We have reported the synthesis of a new π-conjugated molecule, azabuckybowl, which has a curved structure and contains a hetero atom inside. Based on the knowledge obtained from its synthesis, we attempted to synthesize a borabuckybowl, which has been considered to be the most difficult to synthesize. In the process, they succeeded in synthesizing azabuckybowl-PBI complexes that exhibit intramolecular charge transfer, and found results suggesting the construction of an unusual stacking structure in which curved surfaces and planes are stacked on top of each other. Furthermore, a novel synthetic method for terphenyl derivatives, which are precursors for borabuckybowl synthesis, was successfully developed.

Academic Significance and Societal Importance of the Research Achievements

曲面構造をもつπ共役分子は古くから合成が行われているが、多くは炭素または水素原子のみで構成されており、ヘテロ元素を含むものはほとんどない。合成において、ヘテロ元素が脱離しやすい、空気酸化や水分の影響を受けて壊れてしまう点が問題であった。今回、その中で最難関のホウ素を含む曲面分子の合成に挑んだ。その結果、有用な前駆体の合成に成功した。さらに、目的化合物の機能発現のモデルとなる分子を合成し、有機エレクトロニクスデバイスに応用可能な新規な知見を得ることに成功した。これらの成果はこれまで応用が不明瞭であった曲面分子の可能性を広げるものであり、新たな有機材料の創出につながる重要な成果である。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (10 results)

All 2021 2020 2019

All Journal Article (4 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 4 results) Presentation (6 results) (of which Int'l Joint Research: 6 results,  Invited: 6 results)

  • [Journal Article] Heteroatoms in bowl-shaped polycyclic aromatic hydrocarbons: Synthesis and structures2021

    • Author(s)
      Satoru Hiroto
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 6 Pages: 1146-1155

    • DOI

      10.1246/cl.200965

    • NAID

      130008053375

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Helical Pitch Dependent Optical Properties of π-Extended Aza[5]helicene Radical Cations2020

    • Author(s)
      Satoru Hiroto
    • Journal Title

      Bull. Chem. Soc. Jpn.

      Volume: 93 Issue: 11 Pages: 1334-1339

    • DOI

      10.1246/bcsj.20200181

    • NAID

      130007939764

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Regioselective Desilylation of a pi-Extended Aza[5]helicene Web of Science2019

    • Author(s)
      Ushiyama, Ayako; Shinokubo, Hiroshi; Hiroto, Satoru
    • Journal Title

      Chem. Lett.

      Volume: 48 Issue: 9 Pages: 1069-1069

    • DOI

      10.1246/cl.190369

    • NAID

      130007703012

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Amplified Heavy-Atom Free Phosphorescence from Meta-Dimethoxy Difluoroboron β-Diketonate Charge-Transfer Materials2019

    • Author(s)
      C. DeRosa, S. Hiroto, C. L. Fraser
    • Journal Title

      J. Phys. Chem. C

      Volume: 123 Issue: 33 Pages: 20488-20496

    • DOI

      10.1021/acs.jpcc.9b05736

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Twisted porphyrin oligomers: Beta-substituents and metal effect on their structures and electrochemical properties2021

    • Author(s)
      Satoru Hiroto
    • Organizer
      239th ECS Meeting
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] π-Extended helical-shaped pyrroles: Synthesis and redox responsibilities2021

    • Author(s)
      Satoru Hiroto
    • Organizer
      ICPP-11
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Regioselective functionalizations and properties of π-extended aza[5]helicenes2019

    • Author(s)
      Satoru Hiroto
    • Organizer
      the 12th Japan-Taiwan Bilateral Symposium on “Architecture of Functional Organic Molecules”
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and redox switching properties of nitrogen-containing three-dimensional π-conjugated molecules2019

    • Author(s)
      Satoru Hiroto
    • Organizer
      IUPAC 15th International Conference on Novel Materials and their Synthesis
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Effect of nitrogen atom on curved π-surface: Synthesis, supramolecular and redox properties2019

    • Author(s)
      Satoru Hiroto
    • Organizer
      Academia Sinica
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and redox properties of heteroatom containing helical π-conjugated molecules2019

    • Author(s)
      Satoru Hiroto
    • Organizer
      The 18th Asian Chemical Congress
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited

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Published: 2019-07-04   Modified: 2023-01-30  

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