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Bottom-up Synthesis of n-Type Semiconductive Non-planar Nanographenes

Research Project

Project/Area Number 19K22112
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 28:Nano/micro science and related fields
Research InstitutionNara Institute of Science and Technology

Principal Investigator

Aratani Naoki  奈良先端科学技術大学院大学, 先端科学技術研究科, 准教授 (60372562)

Project Period (FY) 2019-06-28 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2020: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Fiscal Year 2019: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywords有機化学 / 複合材料 / アセン / 有機半導体 / ナノグラフェン / ナノカーボン / 曲面π電子系
Outline of Research at the Start

本研究課題では、「n型半導体特性を有するシート型炭化水素」の開発を目指し、構造の明確な、分子として取り扱うことのできる新しいナノカーボンマテリアルの科学を探究する。球状分子のフラーレンは分子間の接触面積が小さく分子間相互作用が極端に限られ、またほとんどの溶媒に対して難溶性である。本研究ではこれらの課題解決に向け、炭素シートを“曲げる”ことにより溶解性を向上させ、また置換基を導入しないことで固体中での良好な積層を妨げ無いようにする。

Outline of Final Research Achievements

We have been working on the functionalization of polycyclic aromatic hydrocarbons (PAHs) by introducing substituents. In this research project, we have achieved the creation of curved π-conjugated systems as fullerene expansion diagrams by π-extension of the curved π-conjugated system, corannulene, as originally intended. Specifically, we succeeded in controlling the absorption spectrum and the fluorescence quantum yield by expanding 10 carbons from corannulene, and by expanding 20 carbons from corannulene. We found charge-transfer type absorption and fluorescence spectra, which are not seen in the case of corannulene alone. In particular, the latter is a property that has been overlooked in conventional π-conjugated compounds, and is a discovery that will have a major impact on future molecular design.

Academic Significance and Societal Importance of the Research Achievements

良く電流を流す有機物は溶けにくい、という化学の常識に挑戦し、研究期間全体を通して、非常にシンプルな炭素シート状化合物の分子設計から様々な特性を引き出すことができた。本研究では、炭素シートを曲げることで溶解性が向上することに着目し、効果的に5員環を導入することで曲面と電子受容性を同時に獲得する戦略に基づき、ボウル型分子であるコラニュレンの縮環多量体の合成により、新規有機n型半導体化合物群の開発に成功した。

Report

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

    (28 results)

All 2021 2020 2019 Other

All Journal Article (11 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 11 results,  Open Access: 2 results) Presentation (16 results) (of which Invited: 2 results) Remarks (1 results)

  • [Journal Article] Synthesis and Evaluation of Charge Transport Property of Ethynylene‐Bridged Anthracene Oligomers2021

    • Author(s)
      Zhu Juanjuan、Hayashi Hironobu、Chen Meng、Xiao Chengyi、Matsuo Kyohei、Aratani Naoki、Zhang Lei、Yamada Hiroko
    • Journal Title

      Macromolecular Chemistry and Physics

      Volume: - Issue: 11 Pages: 2100024-2100024

    • DOI

      10.1002/macp.202100024

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Direct borylation of terrylene and quaterrylene2020

    • Author(s)
      Kano Haruka、Uehara Keiji、Matsuo Kyohei、Hayashi Hironobu、Yamada Hiroko、Aratani Naoki
    • Journal Title

      Beilstein Journal of Organic Chemistry

      Volume: 16 Pages: 621-627

    • DOI

      10.3762/bjoc.16.58

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] A Directly-linked Cyclic Pyrene Tetramer as a Back-to-back Receptor for Two Fullerenes2020

    • Author(s)
      Kurosaki Ryo、Matsuo Kyohei、Hayashi Hironobu、Yamada Hiroko、Aratani Naoki
    • Journal Title

      Chemistry Letters

      Volume: 49 Issue: 8 Pages: 892-895

    • DOI

      10.1246/cl.200233

    • NAID

      130007884706

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Visible‐Light‐Induced Heptacene Generation under Ambient Conditions: Utilization of Single‐crystal Interior as an Isolated Reaction Site2020

    • Author(s)
      Hayashi Hironobu、Hieda Nao、Yamauchi Mitsuaki、Chan Yee Seng、Aratani Naoki、Masuo Sadahiro、Yamada Hiroko
    • Journal Title

      Chemistry - A European Journal

      Volume: 26 Issue: 66 Pages: 15079-15083

    • DOI

      10.1002/chem.202002155

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Pot Synthesis of a Cyclic Pyrene Octamer from Two Bifunctionalized Pyrene Monomers2020

    • Author(s)
      Yamada Hiroko、Aratani Naoki、Mei Peifeng、Kurosaki Ryo、Matsumoto Akinobu
    • Journal Title

      Synthesis

      Volume: 53 Issue: 02 Pages: 344-347

    • DOI

      10.1055/s-0040-1705950

    • NAID

      120007169564

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cyclic butadiyne-linked porphyrin(2.1.2.1) oligomers2020

    • Author(s)
      Kuzuhara Daiki、Furukawa Wataru、Aratani Naoki、Yamada Hiroko
    • Journal Title

      Journal of Porphyrins and Phthalocyanines

      Volume: 24 Issue: 01n03 Pages: 489-497

    • DOI

      10.1142/s1088424619501931

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a Porphyrin(2.1.2.1) Nanobelt and its Ability to Bind Fullerene2019

    • Author(s)
      Songlin Xue, Daiki Kuzuhara,* Naoki Aratani, Hiroko Yamada*
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 7 Pages: 2069-2072

    • DOI

      10.1021/acs.orglett.9b00329

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] A remarkably strained cyclopyrenylene trimer that undergoes metal-free direct oxygen insertion into the biaryl C-C σ-bond2019

    • Author(s)
      Kurosaki Ryo、Hayashi Hironobu、Suzuki Mitsuharu、Jiang Julong、Hatanaka Miho、Aratani Naoki、Yamada Hiroko
    • Journal Title

      Chemical Science

      Volume: 10 Issue: 28 Pages: 6785-6790

    • DOI

      10.1039/c9sc01777a

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Control of Aromaticity and cis ‐/ trans ‐Isomeric Structure of Non‐Planar Hexaphyrin(2.1.2.1.2.1) and Metal Complexes2019

    • Author(s)
      Xue Songlin、Kuzuhara Daiki、Aratani Naoki、Yamada Hiroko
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 36 Pages: 12524-12528

    • DOI

      10.1002/anie.201906946

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] 2,7,12,17-Tetra(2,5-thienylene)-substituted porphycenes2019

    • Author(s)
      Kuzuhara Daiki、Nakaoka Haruka、Matsuo Kyohei、Aratani Naoki、Yamada Hiroko
    • Journal Title

      Journal of Porphyrins and Phthalocyanines

      Volume: 23 Issue: 07n08 Pages: 898-907

    • DOI

      10.1142/s1088424619500743

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Torsional chirality generation based on cyclic oligomers constructed from an odd number of pyrenes2019

    • Author(s)
      Kurosaki Ryo、Suzuki Mitsuharu、Hayashi Hironobu、Fujiki Michiya、Aratani Naoki、Yamada Hiroko
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 65 Pages: 9618-9621

    • DOI

      10.1039/c9cc03123e

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] π拡張フェロセンの合成と物性2021

    • Author(s)
      森本 裕詞、松尾 恭平、山田 容子、荒谷 直樹
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 5,9-直接結合型環状ピレン多量体の合成2021

    • Author(s)
      黒崎 澪、山田 容子、荒谷 直樹
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 炭素原子17 個分の幅を有するアームチェア型グラフェンナノリボンの基板上合成2021

    • Author(s)
      林 宏暢, 山口 淳一, 實宝 秀幸, 塩足 亮隼, 大伴 真名歩, 荒谷 直樹, 大淵 真里, 杉本 宜昭, 佐藤 信太郎, 山田 容子
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] N = 17アームチェアエッジグラフェンナノリボンの電子状態評価2021

    • Author(s)
      山口 淳,林 宏暢,實宝 秀幸,塩足 亮隼,大伴 真名歩,荒谷 直樹,大淵 真理,杉本 宜昭,山田 容子,佐藤 信太郎
    • Organizer
      応用物理学会春季学術講演会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 2,2’-直接結合ペリレン二量体の合成と光物性2020

    • Author(s)
      藤田隆一・松尾恭平・林宏暢・山田容子・荒谷直樹
    • Organizer
      第10回CSJ化学フェスタ 2020
    • Related Report
      2020 Annual Research Report
  • [Presentation] C70への二重付加反応によるキラルフラーレンの合成2020

    • Author(s)
      加納 春華・藤木 道也・山田 容子・荒谷 直樹
    • Organizer
      基礎有機化学会 若手オンラインシンポジウム (第0回)
    • Related Report
      2020 Annual Research Report
  • [Presentation] 二重付加反応によるキラルフラーレンC70の合成と光物性2020

    • Author(s)
      加納春華・藤木道也・山田容子・荒谷直樹
    • Organizer
      2020年web光化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 高歪み環状ピレン3 量体の特異な光物性2020

    • Author(s)
      黒崎 澪 ・ 畑中 美穂 ・ 山田 容子 ・ 荒谷 直樹
    • Organizer
      2020年web光化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 2つのナノ空間をもつ環状ピレン多量体による分子認識2020

    • Author(s)
      黒崎 澪・山田 容子・荒谷 直樹
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] C70 への二重付加反応によるキラルフラーレンの合成と光物性2020

    • Author(s)
      加納春華・藤木道也・山田容子・荒谷直樹
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 高歪み[3]シクロ-1,8-ピレニレンの合成と炭素-炭素結合開裂反応2019

    • Author(s)
      黒崎澪・畑中美穂・荒谷直樹・山田容子
    • Organizer
      第30回基礎有機化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] ユニークな構造をもつπ拡張ピレンの合成と物性2019

    • Author(s)
      荒谷直樹
    • Organizer
      第13回有機π電子系シンポジウム
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] ユニークな構造をもつπ拡張ピレンの合成と物性C70への二重付加反応によるキラルフラーレンの創製2019

    • Author(s)
      加納春華・荒谷直樹・山田容子
    • Organizer
      第13回有機π電子系シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] ユニークな構造をもつピレン誘導体の合成と物性2019

    • Author(s)
      荒谷直樹
    • Organizer
      日本学術振興会 情報科学用有機材料第142委員会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Structure-based Unique Properties of Cyclo-1,8-pyrenylenes2019

    • Author(s)
      Ryo Kurosaki, Naoki Aratani, Hiroko Yamada
    • Organizer
      ISNA18
    • Related Report
      2019 Research-status Report
  • [Presentation] Facile Synthesis of Cyclic π-Conjugated Compounds by Suzuki-Miyaura Cross Coupling Reaction2019

    • Author(s)
      Peifeng Mei, Naoki Aratani, and Hiroko Yamada
    • Organizer
      ISNA18
    • Related Report
      2019 Research-status Report
  • [Remarks] 奈良先端科学技術大学院大学物質創成科学研究科有機光分子科学研究室

    • URL

      https://mswebs.naist.jp/LABs/env_photo_greenmat/index.html

    • Related Report
      2019 Research-status Report

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Published: 2019-07-04   Modified: 2022-01-27  

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