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Generation and function of polarized spins in metal-organic frameworks

Research Project

Project/Area Number 20K21211
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
Research InstitutionKyushu University

Principal Investigator

Yanai Nobuhiro  九州大学, 工学研究院, 准教授 (90649740)

Project Period (FY) 2020-07-30 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
Fiscal Year 2021: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2020: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Keywords光物性 / 金属錯体骨格 / 励起三重項 / スピン
Outline of Research at the Start

分子が光励起されることで生成する励起三重項は室温において大きな電子スピン偏極状態を取ることが可能であるが、そのスピン偏極状態を用いた機能開拓はこれまで十分に行われてこなかった。本研究では、金属錯体骨格中において偏極した光励起三重項の電子スピンを生成し、その偏極状態に基づく新機能創出を目的とする。金属錯体骨格を用いることで色素分子の配置や配列を制御し、励起三重項状態におけるスピンダイナミクスを制御することで、スピン偏極状態を反映した機能の創出を目指す。

Outline of Final Research Achievements

In this study, we focused on the fact that the excited triplet generated by photoexcitation of a molecule produces a large spin polarization at room temperature, and aimed to develop functions using this spin-polarized state. Dye molecules that form spin-polarized excited triplets after photoexcitation were introduced into the metal-organic frameworks as ligands or guest molecules. In the system in which the dye moiety is densely introduced into the metal-organic framework as a ligand, we succeeded in generating not only spin-polarized triplet but also polarized radicals. In the system in which a dye molecule was introduced into the nanopores of the metal-organic framework as a guest, we succeeded in transferring the polarization from the triplet electron spin to the nuclear spin of the drug molecule.

Academic Significance and Societal Importance of the Research Achievements

スピン偏極した励起三重項はこれまでの研究では材料などの評価手段として主に用いられてきたが、本研究ではスピン偏極した励起三重項のポテンシャルを最大限に引き出すことで機能創出に繋げることを試みた。金属錯体骨格中において色素分子の配列を精密に制御することにより、偏極した三重項に加えてラジカルを発生できることを見出し、これは室温における新しい偏極電子スピン生成法として有用であると考えられる。また、三重項電子スピンの偏極をモデル薬物分子の核スピンへと移すことにも成功し、今後の多様な生体分子や薬物分子の高感度NMR, MRI観測に繋がる重要な知見が得られた。

Report

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

    (35 results)

All 2022 2021 2020 Other

All Int'l Joint Research (6 results) Journal Article (13 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 13 results,  Open Access: 3 results) Presentation (14 results) (of which Int'l Joint Research: 6 results,  Invited: 14 results) Remarks (2 results)

  • [Int'l Joint Research] University of Sheffield(英国)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] University of Sheffield(英国)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] Florida State University/Cornell University/University of California, Santa Barbara(米国)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] Pusan National University(韓国)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] Chalmers University of Technology(スウェーデン)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] AMOLF(オランダ)

    • Related Report
      2020 Research-status Report
  • [Journal Article] Heavy metal-free visible-to-UV photon upconversion with over 20% efficiency sensitized by a ketocoumarin derivative2022

    • Author(s)
      Uji Masanori、Harada Naoyuki、Kimizuka Nobuo、Saigo Masaki、Miyata Kiyoshi、Onda Ken、Yanai Nobuhiro
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 10 Issue: 12 Pages: 4558-4562

    • DOI

      10.1039/d1tc05526g

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] In optimized rubrene-based nanoparticle blends for photon upconversion, singlet energy collection outcompetes triplet-pair separation, not singlet fission2022

    • Author(s)
      Bossanyi David G.、Sasaki Yoichi、Wang Shuanqing、Chekulaev Dimitri、Kimizuka Nobuo、Yanai Nobuhiro、Clark Jenny
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 10 Issue: 12 Pages: 4684-4696

    • DOI

      10.1039/d1tc02955j

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Triplet Dynamic Nuclear Polarization of Guest Molecules through Induced Fit in a Flexible Metal-Organic Framework**2022

    • Author(s)
      Fujiwara Saiya、Matsumoto Naoto、Nishimura Koki、Kimizuka Nobuo、Tateishi Kenichiro、Uesaka Tomohiro、Yanai Nobuhiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 61 Issue: 9 Pages: 1-5

    • DOI

      10.1002/anie.202115792

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Design Guidelines for Rigid Epoxy Resins with High Photon Upconversion Efficiency: Critical Role of Emitter Concentration2022

    • Author(s)
      Kashino Tsubasa、Haruki Rena、Uji Masanori、Harada Naoyuki、Hosoyamada Masanori、Yanai Nobuhiro、Kimizuka Nobuo
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: - Issue: 20 Pages: 22771-22780

    • DOI

      10.1021/acsami.1c17021

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Osmium Complex-Chromophore Conjugates with Both Singlet-to-Triplet Absorption and Long Triplet Lifetime through Tuning of the Heavy-Atom Effect2022

    • Author(s)
      Sasaki Yoichi、Yanai Nobuhiro、Kimizuka Nobuo
    • Journal Title

      Inorganic Chemistry

      Volume: - Issue: 16 Pages: 5982-5990

    • DOI

      10.1021/acs.inorgchem.1c03129

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Porphyrins as Versatile, Aggregation-Tolerant, and Biocompatible Polarizing Agents for Triplet Dynamic Nuclear Polarization of Biomolecules2021

    • Author(s)
      T. Hamachi, K. Nishimura, H. Kouno, Y. Kawashima, K. Tateishi, T. Uesaka, N Kimizuka, and N. Yanai
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 12 Issue: 10 Pages: 2645-2650

    • DOI

      10.1021/acs.jpclett.1c00294

    • Related Report
      2021 Annual Research Report 2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Singlet-to-Triplet Absorption for Near-Infrared-to-Visible Photon Upconversion2021

    • Author(s)
      Sasaki Yoichi、Amemori Shogo、Yanai Nobuhiro、Kimizuka Nobuo
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 94 Issue: 6 Pages: 1760-1768

    • DOI

      10.1246/bcsj.20210114

    • NAID

      130008066571

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Design Guidelines to Elongate Spin-Lattice Relaxation Times of Porphyrins with Large Triplet Electron Polarization2021

    • Author(s)
      Yamauchi Akio、Fujiwara Saiya、Nishimura Koki、Sasaki Yoichi、Tateishi Kenichiro、Uesaka Tomohiro、Kimizuka Nobuo、Yanai Nobuhiro
    • Journal Title

      The Journal of Physical Chemistry A

      Volume: 125 Issue: 20 Pages: 4334-4340

    • DOI

      10.1021/acs.jpca.1c01839

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Spin Statistics for Triplet-Triplet Annihilation Upconversion: Exchange Coupling, Intermolecular Orientation, and Reverse Intersystem Crossing2021

    • Author(s)
      Bossanyi David G.、Sasaki Yoichi、Wang Shuangqing、Chekulaev Dimitri、Kimizuka Nobuo、Yanai Nobuhiro、Clark Jenny
    • Journal Title

      JACS Au

      Volume: 1 Issue: 12 Pages: 2188-2201

    • DOI

      10.1021/jacsau.1c00322

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Green-to-UV photon upconversion enabled by new perovskite nanocrystal-transmitter-emitter combination2021

    • Author(s)
      Koharagi Mio、Harada Naoyuki、Okumura Keisuke、Miyano Junji、Hisamitsu Shota、Kimizuka Nobuo、Yanai Nobuhiro
    • Journal Title

      Nanoscale

      Volume: 13 Issue: 47 Pages: 19890-19893

    • DOI

      10.1039/d1nr06588b

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photon upconverting bioplastics with high efficiency and in-air durability2021

    • Author(s)
      Bharmoria Pankaj、Hisamitsu Shota、Sasaki Yoichi、Kang Tejwant Singh、Morikawa Masa-aki、Joarder Biplab、Moth-Poulsen Kasper、Bildirir Hakan、M?rtensson Anders、Yanai Nobuhiro、Kimizuka Nobuo
    • Journal Title

      Journal of Materials Chemistry C

      Volume: Advance Article Issue: 35 Pages: 11655-11661

    • DOI

      10.1039/d1tc00287b

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Up- and down-conversion in molecules and materials2021

    • Author(s)
      Ehrler Bruno、Yanai Nobuhiro、Nienhaus Lea
    • Journal Title

      The Journal of Chemical Physics

      Volume: 154 Issue: 7 Pages: 070401-070401

    • DOI

      10.1063/5.0045323

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Bulk Transparent Photon Upconverting Films by Dispersing High-Concentration Ionic Emitters in Epoxy Resins2021

    • Author(s)
      Kashino Tsubasa、Hosoyamada Masanori、Haruki Rena、Harada Naoyuki、Yanai Nobuhiro、Kimizuka Nobuo
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: 13 Issue: 11 Pages: 13676-13683

    • DOI

      10.1021/acsami.0c23121

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Presentation] トリプレット超核偏極の材料化学2021

    • Author(s)
      楊井伸浩
    • Organizer
      ATI水和ナノ構造研究会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 励起三重項の機能化学2021

    • Author(s)
      楊井伸浩
    • Organizer
      大阪市立大学大学院工学研究科セミナー
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] トリプレット超核偏極の材料化学2021

    • Author(s)
      楊井伸浩
    • Organizer
      量子生命科学会第3回大会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 分子性固体材料におけるトリプレットの活用2021

    • Author(s)
      楊井伸浩
    • Organizer
      物性研短期研究会「分子性固体研究の拡がり:新物質と新現象」
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] Materials chemistry of triplet dynamic nuclear polarization2021

    • Author(s)
      Nobuhiro Yanai
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Functional chemistry of triplet state: photon upconversion and hyperpolarization2021

    • Author(s)
      Nobuhiro Yanai
    • Organizer
      Dept. of Chemistry, University at Albany, SUNY
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 光励起三重項のテンプレートロジーに向けて2021

    • Author(s)
      楊井伸浩
    • Organizer
      日本化学会第102 春季年会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] トリプレット超核偏極における材料化学的アプローチ2021

    • Author(s)
      楊井伸浩
    • Organizer
      よこはまNMR研究会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] NIR-to-Visible Photon Upconversion for Applications in Energy and Biology2020

    • Author(s)
      Nobuhiro Yanai
    • Organizer
      Japan-Taiwan Young Scientists Polymer Symposium, 第69回高分子討論会
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Photon Upconversion and Triplet Dynamic Nuclear Polarization in MOFs2020

    • Author(s)
      Nobuhiro Yanai
    • Organizer
      PRiME 2020 Meeting
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 薩長同盟的光機能性材料開発2020

    • Author(s)
      楊井伸浩
    • Organizer
      第10回CSJ化学フェスタ2020
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] トリプレットの機能化学:フォトン・アップコンバージョンと超核偏極2020

    • Author(s)
      楊井伸浩
    • Organizer
      第5回有機若手ワークショップ, 京都大学
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] Materials chemistry of triplet dynamic nuclear polarization2020

    • Author(s)
      Nobuhiro Yanai
    • Organizer
      The 3rd International Forum on Quantum Metrology and Sensing (IFQMS)
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Solving Challenging Problems in Visible-to-UV and NIR-to-Visible Photon Upconversion by Developing New Dyes2020

    • Author(s)
      Nobuhiro Yanai
    • Organizer
      nanoGe Spring Meeting
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Remarks] 硬くて柔らかいナノ多孔性材料が実現する室温核偏極

    • URL

      https://www.kyushu-u.ac.jp/ja/researches/view/709

    • Related Report
      2021 Annual Research Report
  • [Remarks] 可視光から紫外光へのアップコンバージョン効率の世界記録を大幅に更新

    • URL

      https://www.kyushu-u.ac.jp/ja/researches/view/512

    • Related Report
      2020 Research-status Report

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Published: 2020-08-03   Modified: 2023-01-30  

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