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Paradigm Shift for Observation of Phosphorescence-Derived Circularly Polarized Luminescence in the near infrared region

Research Project

Project/Area Number 18K19063
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 32:Physical chemistry, functional solid state chemistry, and related fields
Research InstitutionKeio University

Principal Investigator

Hasobe Taku  慶應義塾大学, 理工学部(矢上), 教授 (70418698)

Project Period (FY) 2018-06-29 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2019: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2018: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywords円偏光発光 / キラル分光特性 / 近赤外領域 / 光物性 / 近赤外発光
Outline of Final Research Achievements

A homoleptic zinc(II) helicate organized by a pair of achiral dipyrromethene ligands through zinc(II)-coordination were systematically synthesized to estimate the chiroptical properties. This zinc complex demonstrated strong exciton-coupled chiroptical responses from the helical configuration with a strong absorption dissymmetry factor |gabs| (up to 0.20). More importantly, an intense polarized luminescence in the far-red region (700-850 nm) with a fluorescence quantum yield ΦFL of 0.23 was observed for this helicate with a dissymmetry factor |glum| of 0.022, the largest value among the rare earth- and precious metal-free small molecules. These unprecedentedly large g values were supported by theoretical calculations. Additionally, singlet fission using acene derivatives for phosphorescence-derived circularly polarized luminescence in the near infrared region was also observed.

Academic Significance and Societal Importance of the Research Achievements

円偏光発光(CPL)は3Dディスプレイだけでなく、セキュリティペイントや光通信を含む高度光情報プロセシングへの展開が期待されている。しかしながら、これらに必要な近赤外領域でのCPLの報告例は皆無である。本研究では非平面型ジピロメテン誘導体を用いて安定にキラル保持が可能な亜鉛錯体を合成し、円二色性吸収 (CD) およびCPL の各種測定を行った。異方性因子は赤色および近赤外の領域において、gabs : 0.22およびglum: 0.022を達成した。報告されている近赤外領域での有機低分子系のglumとしては最高値を示す結果が得られた。

Report

(5 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (29 results)

All 2021 2020 2019 2018 Other

All Int'l Joint Research (4 results) Journal Article (11 results) (of which Int'l Joint Research: 6 results,  Peer Reviewed: 11 results,  Open Access: 1 results) Presentation (14 results) (of which Int'l Joint Research: 2 results,  Invited: 7 results)

  • [Int'l Joint Research] タンペレ大学(フィンランド)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] タンペレ大(フィンランド)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] タンペレ大学(フィンランド)

    • Related Report
      2019 Research-status Report
  • [Int'l Joint Research] タンペレ工科大学(フィンランド)

    • Related Report
      2018 Research-status Report
  • [Journal Article] Synergetic Role of Conformational Flexibility and Electronic Coupling for Quantitative Intramolecular Singlet Fission2021

    • Author(s)
      Nakamura Shunta、Sakai Hayato、Nagashima Hiroki、Fuki Masaaki、Onishi Kakeru、Khan Ramsha、Kobori Yasuhiro、Tkachenko Nikolai V.、Hasobe Taku
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 125 Issue: 33 Pages: 18287-18296

    • DOI

      10.1021/acs.jpcc.1c04734

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] An Air‐ and Water‐Stable B4N4‐Heteropentalene Serving as a Host Material for a Phosphorescent OLED2021

    • Author(s)
      Kashida Junki、Shoji Yoshiaki、Ikabata Yasuhiro、Taka Hideo、Sakai Hayato、Hasobe Taku、Nakai Hiromi、Fukushima Takanori
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 44 Pages: 23812-23818

    • DOI

      10.1002/anie.202110050

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Organic-Inorganic Hybrid Molecular Architectures Utilizing Self-assembled Monolayers for Singlet Fission and Light Energy Conversion2021

    • Author(s)
      T. Hasobe
    • Journal Title

      Chem. Lett.

      Volume: 50 Issue: 4 Pages: 615-622

    • DOI

      10.1246/cl.200858

    • NAID

      130008025766

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Excimer Formation of Aryl Iodides Chemisorbed on Gold Nanoparticles for the Significant Enhancement of Photoluminescence2020

    • Author(s)
      P. Maity, K. Sasai R. N. Dhital, H. Sakai T. Hasobe, H. Sakurai
    • Journal Title

      J. Phys. Chem. Lett.

      Volume: 11 Issue: 4 Pages: 1199-1203

    • DOI

      10.1021/acs.jpclett.9b03557

    • Related Report
      2020 Research-status Report 2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Geometries and Terahertz Motions Driving Quintet Multiexcitons an Ultimate Triplet-Triplet Disociations via the Intramolecular Singlet Fissions2020

    • Author(s)
      Y. Kobori, M. Fuki, S. Nakamura, T. Hasobe
    • Journal Title

      J. Phys. Chem. B

      Volume: 124 Issue: 42 Pages: 9411-9419

    • DOI

      10.1021/acs.jpcb.0c07984

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Systematic Control of Structural and Photophysical Properties of π‐Extended Mono‐ and Bis‐BODIPY Derivatives2020

    • Author(s)
      H. Ito, H. Sakai, H. Suzuki, J. Kawamata, T. Hasobe
    • Journal Title

      Chem. Eur. J.

      Volume: 26 Issue: 1 Pages: 316-325

    • DOI

      10.1002/chem.201904282

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Controlled Orientations of Neighboring Tetracene Units by Mixed Self-Assembled Monolayers on Gold Nanoclusters for High-Yield and Long-Lived Triplet Excited States through Singlet Fission2019

    • Author(s)
      T. Saegusa, H. Sakai, H. Nagashima, S. Nakamura, Y. Kobori, N. V. Tkachenko, T. Hasobe
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Issue: 37 Pages: 14720-14727

    • DOI

      10.1021/jacs.9b06567

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Significant Enhancement of Absorption and Luminescence Dissymmetry Factors in the Far-Red Region: A Zinc(II) Homoleptic Helicate Formed by a Pair of Achiral Dipyrromethene Ligands2018

    • Author(s)
      Ito Hiroaki、Sakai Hayato、Okayasu Yoshinori、Yuasa Junpei、Mori Tadashi、Hasobe Taku
    • Journal Title

      Chemistry - A European Journal

      Volume: 24 Issue: 63 Pages: 16889-16894

    • DOI

      10.1002/chem.201804171

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Quantitative Sequential Photoenergy Conversion Process from Singlet Fission to Intermolecular Two-Electron Transfers Utilizing Tetracene Dimer2018

    • Author(s)
      Nakamura Shunta、Sakai Hayato、Nagashima Hiroki、Kobori Yasuhiro、Tkachenko Nikolai V.、Hasobe Taku
    • Journal Title

      ACS Energy Letters

      Volume: 4 Issue: 1 Pages: 26-31

    • DOI

      10.1021/acsenergylett.8b01964

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] High‐Yield Generation of Triplet Excited States by an Efficient Sequential Photoinduced Process from Energy Transfer to Singlet Fission in Pentacene‐Modified CdSe/ZnS Quantum Dots2018

    • Author(s)
      Sakai Hayato、Inaya Ryutaro、Tkachenko Nikolai V.、Hasobe Taku
    • Journal Title

      Chemistry - A European Journal

      Volume: 24 Issue: 64 Pages: 17062-17071

    • DOI

      10.1002/chem.201803257

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Multiexciton Dynamics Depending on Intramolecular Orientations in Pentacene Dimers: Recombination and Dissociation of Correlated Triplet Pairs2018

    • Author(s)
      Sakai Hayato、Inaya Ryutaro、Nagashima Hiroki、Nakamura Shunta、Kobori Yasuhiro、Tkachenko Nikolai V.、Hasobe Taku
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 9 Issue: 12 Pages: 3354-3360

    • DOI

      10.1021/acs.jpclett.8b01184

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 新規 BN-ヘテロペンタレン 誘導体の合成と性質2021

    • Author(s)
      菓子田惇輝・庄子良晃・五十幡 康弘・高秀雄・酒井隼人・羽曾部 卓・中井浩巳・福島孝典
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ボロンジピロメテン集合体の構造制御による多重発光発現とキラル分光特性2021

    • Author(s)
      酒井隼人・中嶋琢也・河合壯・ 羽曾部卓
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 機能性リンカーを有するアセン二量体の合成と光物性評価2020

    • Author(s)
      津田 絢斗、酒井 隼人、羽曾部 卓
    • Organizer
      2020web光化学討論会
    • Related Report
      2020 Research-status Report
  • [Presentation] ビナフチル架橋アセンニ量体の励起ダイナミクス評価2020

    • Author(s)
      酒井 隼人 ・Tkachenko Nikolai・羽曾部 卓
    • Organizer
      2020web光化学討論会
    • Related Report
      2020 Research-status Report
  • [Presentation] Construction of Organic and Inorganic Hybrid Nanomaterials utilizing Acene Derivatives for Efficient Singlet Fission2019

    • Author(s)
      T. Hasobe and H. Sakai
    • Organizer
      235th The Electrochemical Society Center Meeting
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 多重分子による協同的励起状態制御と電気化学測定2019

    • Author(s)
      羽曾部 卓
    • Organizer
      2019電気化学会秋季大会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 多重分子の協同的相互作用による励起状態制御の新展開2019

    • Author(s)
      羽曾部 卓
    • Organizer
      東工大 超分子分析化学セミナー9
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 共有結合で連結したヘキサセン二量体の合成と一重項分裂の観測2019

    • Author(s)
      中村 俊太・酒井 隼人 ・Tkachenko Nikolai・羽曾部 卓
    • Organizer
      2019光化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] 不斉配位子で置換したボロンジピロメテン誘導体の合成とキラル分光特性2019

    • Author(s)
      鈴木 悠大 ・酒井 隼人 ・羽曾部 卓
    • Organizer
      2019光化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] キラル連結部位で架橋したボロンジピロメテン二量体の合成と分光特性2019

    • Author(s)
      津田 絢斗・酒井 隼人・羽曾部 卓
    • Organizer
      第99日本化学会春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 分子材料における励起ダイナミクス制御の新展開2019

    • Author(s)
      羽曾部 卓
    • Organizer
      超分子創製化学セミナー
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] High-yield singlet fission and sequential photoinduced process in acene-based molecular assemblies2019

    • Author(s)
      Taku Hasobe
    • Organizer
      International Workshop Photofunctional Materials Using Spin Degrees of Freedom: Interplay among synthesis, measurement, and theory.
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 光機能発現に向けた有機材料の設計戦略と応用展開2018

    • Author(s)
      羽曾部 卓
    • Organizer
      電気化学会関東支部主催 第54回学際領域セミナー「光電気化学的応用のためのナノマテリアル設計」
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] 二次元π共役分子および集合体の励起ダイナミクス制御2018

    • Author(s)
      羽曾部 卓
    • Organizer
      日本化学会低次元系光機能材料研究会 第7回研究講演会―二次元構造を有するπ電子系の光・電子機能―
    • Related Report
      2018 Research-status Report
    • Invited

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Published: 2018-07-25   Modified: 2023-01-30  

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