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Understanding of structure-property relationship of polyacenes and its application to on-surface synthesis of nanocarbons

Research Project

Project/Area Number 20H02816
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 35030:Organic functional materials-related
Research InstitutionNational Institute for Materials Science (2022)
Nara Institute of Science and Technology (2020-2021)

Principal Investigator

Hironobu Hayashi  国立研究開発法人物質・材料研究機構, 先端材料解析研究拠点, 主任研究員 (00736936)

Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000)
Fiscal Year 2022: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2021: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000)
Fiscal Year 2020: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000)
Keywords高次アセン / 基板上合成 / 構造物性相関 / ナノカーボン / グラフェンナノリボン / 前駆体 / 環状分子 / 表面合成 / アセン / 光反応 / ナノ構造体 / ナノカーボン材料 / 前駆体法
Outline of Research at the Start

ベンゼン環が直線状に縮合された高次アセンの構造・物性・反応性相関の本質的理解は、所望の物性を有するナノカーボン材料の革新的合成法開拓に結びつくのではないだろうか?本研究では、炭素と水素のみから構成される従来型の単純高次アセンではなく、シンプルな置換基やヘテロ原子を導入した高次アセン誘導体の合成を行い、その構造物性相関に関する実験的知見の獲得を目指す。また、加熱が主流である従来の基板上合成とは異なる、光照射を契機とした基板上合成法を開拓する。加えて、昇華の必要性や細かな構造制御が不得意という制約のない、汎用性に富む新規基板上合成法を確立し、革新的ナノカーボン合成の実現を目指す。

Outline of Final Research Achievements

Polyacenes, which have linearly fused benzene rings, are known to exhibit not only high charge transport properties but also biradical characters in the ground state. Additionally, they are useful as precursors for nanocarbon materials. In this study, we have developed a synthetic method for unstable polyacenes under anaerobic conditions such as interior of a single crystal and ultra-high vacuum conditions, and successfully unveiled the structure-property relationship of polyacenes. Furthermore, we created a “foothold” for the synthesis of graphene nanoribbons in a simple manner that does not require conventional sublimation/heating processes of precursor molecules under ultra-high vacuum conditions.

Academic Significance and Societal Importance of the Research Achievements

高次アセンの合成法確立と物性相関理解は、次世代デバイスへの応用が期待される有機半導体・ナノカーボン材料を設計する上で有用な知見である。また、高次アセンの基板上合成研究の過程で得られた、高次にpi共役系が拡張された予想外のナノ分子生成の発見は、独自のナノ構造体創成法につながる成果である。また、新しい基板上光反応性の開拓・理解、簡便なプロセスを用いたナノ構造体・ナノカーボン材料構築法の開拓は、従来の手法を用いた研究とは方向性の異なる研究への発展を促すものである。

Report

(4 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • Research Products

    (42 results)

All 2023 2022 2021 2020 Other

All Int'l Joint Research (6 results) Journal Article (17 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 17 results,  Open Access: 7 results) Presentation (18 results) (of which Int'l Joint Research: 4 results,  Invited: 3 results) Book (1 results)

  • [Int'l Joint Research] Universidad Autonoma de Madrid/IMDEA-Nanociencia(スペイン)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] 北京化工大学(中国)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] Empa(スイス)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] Universidad Autonoma de Madrid/IMDEA-Nanociencia(スペイン)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] 北京化工大学(中国)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] Empa(スイス)

    • Related Report
      2020 Annual Research Report
  • [Journal Article] An Atropisomerism Study of Large Cycloarylenes: [n]Cyclo‐4,10‐Pyrenylenes’ Case2023

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

      Chemistry - A European Journal

      Volume: - Issue: 24

    • DOI

      10.1002/chem.202203848

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Series of Soluble Planar Oligorylenes up to Hexarylene2023

    • Author(s)
      Fujita Ryuichi、Yoshida Shoko、Kano Haruka、Matsuo Kyohei、Hayashi Hironobu、Yamada Hiroko、Aratani Naoki
    • Journal Title

      Chinese Journal of Chemistry

      Volume: 41 Issue: 9 Pages: 1023-1027

    • DOI

      10.1002/cjoc.202200692

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polyazaacene and Cyclazaacene Precursors Synthesized by Dehydration Condensation from a Versatile Bis‐ <i>α</i> ‐diketone Unit Having an Anthracene Skeleton2022

    • Author(s)
      Chan Yee Seng、Hayashi Hironobu、Sato Shizuka、Kasahara Shoma、Matsuo Kyohei、Aratani Naoki、Yamada Hiroko
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2022 Issue: 38

    • DOI

      10.1002/ejoc.202200621

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] On-surface synthesis of hydroxy-functionalized graphene nanoribbons through deprotection of methylenedioxy groups2022

    • Author(s)
      Ohtomo Manabu、Hayashi Hironobu、Shiotari Akitoshi、Kawamura Mayu、Hayashi Ryunosuke、Jippo Hideyuki、Yamaguchi Junichi、Ohfuchi Mari、Aratani Naoki、Sugimoto Yoshiaki、Yamada Hiroko、Sato Shintaro
    • Journal Title

      Nanoscale Advances

      Volume: 4 Issue: 22 Pages: 4871-4879

    • DOI

      10.1039/d2na00031h

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of oligoacenes using precursors for evaluation of their electronic structures2022

    • Author(s)
      Yamada Hiroko、Hayashi Hironobu
    • Journal Title

      Photochemical & Photobiological Sciences

      Volume: 21 Issue: 8 Pages: 1511-1532

    • DOI

      10.1007/s43630-022-00235-x

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Phosphaacene as a structural analogue of thienoacenes for organic semiconductors2022

    • Author(s)
      Matsuo Kyohei、Okumura Rina、Hayashi Hironobu、Aratani Naoki、Jinnai Seihou、Ie Yutaka、Saeki Akinori、Yamada Hiroko
    • Journal Title

      Chemical Communications

      Volume: 58 Issue: 98 Pages: 13576-13579

    • DOI

      10.1039/d2cc05122b

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis and properties of 10,20-bis(triisopropylsilylethynyl)-tetrabenzo-5,15-diazaporphine2022

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

      Journal of Porphyrins and Phthalocyanines

      Volume: - Issue: 01n04 Pages: 136-144

    • DOI

      10.1142/s1088424622500766

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Single crystal field-effect transistor of tetrabenzoporphyrin with a one-dimensionally extended columnar packing motif exhibiting efficient charge transport properties2022

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

      Journal of Materials Chemistry C

      Volume: 10 Issue: 7 Pages: 2527-2531

    • DOI

      10.1039/d1tc03547a

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] On-surface synthesis and characterization of nitrogen-substituted undecacenes2022

    • Author(s)
      Eimre Kristjan、Urgel Jose I.、Hayashi Hironobu、Di Giovannantonio Marco、Ruffieux Pascal、Sato Shizuka、Otomo Satoru、Chan Yee Seng、Aratani Naoki、Passerone Daniele、Groning Oliver、Yamada Hiroko、Fasel Roman、Pignedoli Carlo A.
    • Journal Title

      Nature Communications

      Volume: 13 Issue: 1 Pages: 511-511

    • DOI

      10.1038/s41467-022-27961-1

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Facile Post-synthesis and Redox Behavior of π-Expanded Ferrocene and ansa-Ferrocene2022

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

      Chemistry Letters

      Volume: 51 Issue: 4 Pages: 428-430

    • DOI

      10.1246/cl.220011

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient photogeneration of long acenes on nanostructured graphene2021

    • Author(s)
      Cosme G. Ayani, Michele Pisarra, Jos_ I. Urgel, Juan Jes_s Navarro, Cristina D_az, Hironobu Hayashi, Hiroko Yamada, Fabian Calleja, Rodolfo Miranda, Roman Fasel, Fernando Mart_n*, Amadeo L. V_zquez de Parga*
    • Journal Title

      Nanoscale Horizons

      Volume: 6 Issue: 9 Pages: 744-750

    • DOI

      10.1039/d1nh00184a

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Mirror‐Image Cofacial Coronene Dimers Characterized by CD and CPL Spectroscopy: A Twisted Bilayer Nanographene2021

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

      ChemPhotoChem

      Volume: 5 Issue: 11 Pages: 974-978

    • DOI

      10.1002/cptc.202100166

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of 10,20-substituted tetrabenzo-5,15-diazaporphyrin copper complexes from soluble precursors2021

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

      Journal of Porphyrins and Phthalocyanines

      Volume: 25 Issue: 10n12 Pages: 1186-1192

    • DOI

      10.1142/s1088424621501194

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Deep-red circularly polarised luminescent C70 derivatives2021

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

      Scientific Reports

      Volume: 11 Issue: 1 Pages: 12072-12072

    • DOI

      10.1038/s41598-021-91451-5

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Buckyball as an Electron Donor in a Dyad of C60 and Xanthene Dye2021

    • Author(s)
      Haruka Kano, Kyohei Matsuo, Hironobu Hayashi, Kosaku Kato, Akira Yamakata, Hiroko Yamada, Naoki Aratani
    • Journal Title

      European Journal of Organic Chemistry

      Volume: - Issue: 23 Pages: 3377-3381

    • DOI

      10.1002/ejoc.202100276

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [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] 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
  • [Presentation] ジケトンとジアミンとの脱水縮合反応を用いた大環状分子の合成2023

    • Author(s)
      南野直人、林宏暢、荒谷直樹、山田容子
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 高効率な電荷輸送特性を示す一次元カラム構造を形成したテトラベンゾポルフィリンの単結晶電界効果トランジスタ2023

    • Author(s)
      林 宏暢、Zhu Juanjuan、松尾 恭平、荒谷 直樹、山田 容子
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] トリプチセン誘導体を利用したポーラスナノシートの合成2023

    • Author(s)
      山本 築、林 宏暢、松尾恭平、荒谷 直樹、山田 容子
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] On-surface synthesis and characterization of tetraazaundecacene and its derivatives2022

    • Author(s)
      Hironobu Hayashi, Hiroko Yamada
    • Organizer
      第63回 フラーレン・ナノチューブ・グラフェン 総合シンポジウム
    • Related Report
      2022 Annual Research Report
  • [Presentation] 可逆的ボロン酸エステル形成を利用した環状分子の合成:異性体の分離効果2022

    • Author(s)
      笠原彰真、林 宏暢、荒谷 直樹、山田 容子
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Polyazaacenes Generation by Using Precursor Methods2022

    • Author(s)
      Yee Seng CHAN, Hironobu Hayashi, Naoki Aratani, Hiroko Yamada
    • Organizer
      241st ECS Meeting
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] On-surface synthesis of armchair-type graphene nanoribbons by using p-dihalobenzene-based precursors2022

    • Author(s)
      Hironobu Hayashi, Junichi Yamaguchi, Takayuki Okumura, Daichi Kishimoto, Hideyuki Jippo, Kyohei Matsuo, Naoki Aratani, Mari Ohfuchi, Sintaro Sato, Hiroko Yamada
    • Organizer
      International Workshop On-Surface Synthesis (OSS22)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Oligoacenes as Ladder-Type pi-Conjugated Molecules2022

    • Author(s)
      Hironobu Hayashi
    • Organizer
      The 2nd Workshop on Ladder Polymer Science
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Polyazaacene and cyclazaacene precursor synthesis2022

    • Author(s)
      Hironobu Hayashi、Hiroko Yamada
    • Organizer
      11th singapore international chemical conference
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 脱水縮合反応を用いたベルト型環状分子の合成2022

    • Author(s)
      笠原 彰真, 林 宏暢, 荒谷 直樹, 山田 容子
    • Organizer
      日本化学会 第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] フッ素修飾グラフェンナノリボンの部分構造合成2022

    • Author(s)
      岸本 太地, 林 宏暢, 荒谷 直樹, 山田 容子
    • Organizer
      日本化学会 第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] エチニレン架橋されたアセン多量体の合成:ワンポット合成と多段階合成2022

    • Author(s)
      南野 直人, 林 宏暢, 荒谷 直樹, 山田 容子
    • Organizer
      日本化学会 第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ボロン酸と1,2-ジオールとの可逆的ボロン酸エステル形成を利用した環状アントラセン二量体の合成2022

    • Author(s)
      奥村 崇之, 林 宏暢, 荒谷 直樹, 山田 容子
    • Organizer
      日本化学会 第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 基板上合成を用いた含窒素ウンデカセンとその誘導体の合成2022

    • Author(s)
      林 宏暢、山田 容子
    • Organizer
      日本化学会 第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 新規キラルフラーレン合成法の開拓とキロプティカル特性2021

    • Author(s)
      加納春華、林宏暢、松尾恭平、藤木道也、山田容子、荒谷直樹
    • Organizer
      基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ペンタセン前駆体が薄膜中で示す光転化反応の解析2021

    • Author(s)
      方 涛,塩谷 暢貴,冨田 和孝,吉田 茉莉子,下赤 卓史,林 宏暢,山田 容子,長谷川 健
    • Organizer
      第69回応用物理学会春季学術講演会
    • Related Report
      2021 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] 前駆体法を用いた高次アセン合成と機能性材料創出への展開2020

    • Author(s)
      林宏暢
    • Organizer
      ACE Meeting Online II
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Book] Atomically Precise Nanochemistry2023

    • Author(s)
      Hironobu Hayashi、Hiroko Yamada
    • Total Pages
      24
    • Publisher
      Wiley Online Library
    • Related Report
      2022 Annual Research Report

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Published: 2020-04-28   Modified: 2024-01-30  

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