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Enhanced molecular emission characteristics by controlling electronic structure relating to the high order singlet excited state

Research Project

Project/Area Number 18H02046
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 InstitutionThe University of Electro-Communications

Principal Investigator

Hirata Shuzo  電気通信大学, 大学院情報理工学研究科, 准教授 (20552227)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥17,030,000 (Direct Cost: ¥13,100,000、Indirect Cost: ¥3,930,000)
Fiscal Year 2020: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2019: ¥10,140,000 (Direct Cost: ¥7,800,000、Indirect Cost: ¥2,340,000)
Fiscal Year 2018: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Keywords高次一重項励起状態 / 2光子吸収 / 光アップコンバージョン / 室温りん光 / 長寿命室温りん光 / 蓄光 / 三重項励起状態 / スピン軌道相互作用 / Kasha則 / 非放射遷移 / Kashaの法則 / 内部項間 / 分子軌道 / 高次励起状態 / 励起吸収 / 2段階励起
Outline of Final Research Achievements

Electronic structures relating to the high order singlet excited state (Sn) have not been considered to control excitons. Here we enhance photon up-conversion characteristics via two-photon absorption and persistent room-temperature phosphorescence (RTP) characteristics by controlling the electronic structures relating to Sn. The effective separation between electronic structures relating to Sn and that relating to the lowest singlet excited state led to more fluorescence from Sn to allow enhanced photon-up conversion intensity after stepwise two-photon absorption. The enhancement of the transition dipole moment between Sn and the ground state by controlling the Sn electronic structure increases the rate constant of phosphorescence without largely increasing the rate constant of nonradiative transition from the lowest triplet excited state, resulting in a large increase of RTP yield with keeping long RTP lifetime.

Academic Significance and Societal Importance of the Research Achievements

生体イメージング用の発光分子プローブでは、個々の分子が分子レベルで反応に作用する必要があるが、逐次型2光子吸収によって光アップコンバージョンを示す分子はより小型な低パワーナノ秒光源での3次元発光イメージングを可能にする技術につながる可能性がある。また高効率長寿命室温りん光分子の既存の蓄光材料、化学発光材料、放射線材料と比較して瞬間的につよい残光の輝度を出す特性は、既存の材料や技術では困難であった高解像イメージングと自家蛍光フリーを両立する非接触イメージング技術領域を開拓することにつながることが期待される。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (44 results)

All 2021 2020 2019 2018

All Journal Article (19 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 19 results,  Open Access: 6 results) Presentation (18 results) (of which Int'l Joint Research: 6 results,  Invited: 13 results) Book (5 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Key of Suppressed Triplet Nonradiative Transition-Dependent Chemical Backbone for Spatial Self-Tunable Afterglow2021

    • Author(s)
      Indranil Bhattacharjee, Kikuya Hayashi, Shuzo Hirata*
    • Journal Title

      JACS Au

      Volume: in press

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Chiral Approach to Investigate Mechanism of Highly Efficient Thermally Activated Delayed Fluorescence2021

    • Author(s)
      Kikuya Hayashi, Arimasa Matsumoto, Shuzo Hirata*
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 14 Pages: 1738-1741

    • DOI

      10.1039/d0cc08064k

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Vibrational Radiationless Transition from Triplet States of Chromophores at Room Temperature2021

    • Author(s)
      Shuzo Hirata*, Indranil Bhattacharjee
    • Journal Title

      The Journal of Physical Chemistry A

      Volume: 125 Issue: 3 Pages: 885-894

    • DOI

      10.1021/acs.jpca.0c09410

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Phosphorescence Quenching of Heavy-atom-free Dopant Chromophores Triggered by Thermally Activated Triplet Exciton Diffusion of Conjugated Crystalline Host2020

    • Author(s)
      Shuzo Hirata*, Hyuman Hara, Indranil Bhattacharjee
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 45 Pages: 25121-25132

    • DOI

      10.1021/acs.jpcc.0c07864

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The Substituent-Induced Symmetry-Forbidden Electronic Transition Allows Significant Optical Limiting under Weak Sky-Blue Irradiance2020

    • Author(s)
      Takuya Kamatsuki, Indranil Bhattacharjee,* and Shuzo Hirata*
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 11 Issue: 20 Pages: 8675-8681

    • DOI

      10.1021/acs.jpclett.0c02694

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Highly efficient persistent room-temperature phosphorescence from heavy atom-free molecules triggered by hidden long phosphorescent antenna2020

    • Author(s)
      Indranil, Bhattacharjee, Shuzo Hirata*
    • Journal Title

      Advanced Materials

      Volume: 32 Issue: 31 Pages: 2001348-2001348

    • DOI

      10.1002/adma.202001348

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Energy localization vs. charge funneling in aggregates of CsPbBr3 perovskite nanocrystals2020

    • Author(s)
      Dharmendar Kumar Sharma*, Shuzo Hirata, Martin Vacha*
    • Journal Title

      Journal of Luminescence

      Volume: 222 Pages: 117119-117119

    • DOI

      10.1016/j.jlumin.2020.117119

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Effect of Tris(trimethylsilyl)silyl Group on the Fluorescence and Triplet Yields of Oligothiophenes2020

    • Author(s)
      Hirata, S.;* Nishio, M.; Uchida, H.; Usuki, T.; Nakae, T.; Miyachi, M.; Yamanoi, Y.;* Nishihara, H.*
    • Journal Title

      J. Phys. Chem. C

      Volume: 124 Issue: 5 Pages: 3277-3286

    • DOI

      10.1021/acs.jpcc.9b10718

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Single-particle electroluminescence of CsPbBr3 perovskite nanocrystals reveals particle-selective recombination and blinking as key efficiency factors2019

    • Author(s)
      Dharmendar Kumar Sharma*, Shuzo Hirata, Martin Vacha*
    • Journal Title

      Nature Communications

      Volume: 10 Issue: 1 Pages: 4499-4499

    • DOI

      10.1038/s41467-019-12512-y

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Roles of Localized Electronic Structures caused by π Degeneracy due to Highly Symmetric Heavy Atom-free Conjugated Molecular Crystals leading to Efficient Persistent Room-temperature Phosphorescence2019

    • Author(s)
      Shuzo Hirata
    • Journal Title

      Advanced Science

      Volume: 6 Pages: 1900410-1900410

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Suppressed Triplet Exciton Diffusion Due to Small Orbital Overlap as a Key Design Factor for Ultralong‐Lived Room‐Temperature Phosphorescence in Molecular Crystals2019

    • Author(s)
      Kaishi Narushima, Yasuhiro Kiyota, Takehiko Mori, Shuzo Hirata, Martin Vacha
    • Journal Title

      Advanced Materials

      Volume: 31 Issue: 10 Pages: 1807268-1807268

    • DOI

      10.1002/adma.201807268

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stark Effect and Environment Induced Modulation of Emission in Single Halide Perovskite Nanocrystals2019

    • Author(s)
      Dharmendar Kumar Sharma, Shuzo Hirata, Vasudevanpillai Biju, Martin Vacha
    • Journal Title

      ACS nano

      Volume: 13 Issue: 1 Pages: 624-632

    • DOI

      10.1021/acsnano.8b07677

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Colorless Semi-aromatic Polyimide Derived from a Sterically Hindered Bromine-Substituted Dianhydride Exhibiting Dual Fluorescent and Phosphorescent Emission2019

    • Author(s)
      Kenta Kanosue, Shuzo Hirata, Martin Vacha, Ramunas Augulis, Vidmantas Gulbinas, Ryohei Ishige, Shinji Ando
    • Journal Title

      Materials Chemistry Frontier

      Volume: 3 Issue: 1 Pages: 39-49

    • DOI

      10.1039/c8qm00409a

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Wavelength-Tunable Band-Edge Photoluminescence of Nonstoichiometric Ag-In-S Nanoparticles via Ga3+ Doping2018

    • Author(s)
      Tatsuya Kameyama, Marino Kishi, Chie Miyamae, Dharmendar Kumar Sharma, Shuzo Hirata, Takahisa Yamamoto, Taro Uematsu, Martin Vacha, Susumu Kuwabata, and Tsukasa Torimoto
    • Journal Title

      ACS Applied Mater. Interfaces

      Volume: 10 Issue: 49 Pages: 42844-42855

    • DOI

      10.1021/acsami.8b15222

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] dentification of Short- and Long-Wavelength Emitting Chlorophylls in Cyanobacterial Photosystem I by Plasmon-Enhanced Single-Particle Spectroscopy at Room Temperature2018

    • Author(s)
      Soya Hatazaki, Dharmendar Kumar Sharma, Shuzo Hirata, Keiji Nose, Tomokazu Iyoda, Adrian Kolsch, Heiko Lokstein, Martin Vacha
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 9 Pages: 6669-6675

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Narrow band-edge photoluminescence from AgInS2 semiconductor nanoparticles by the formation of amorphous III-VI semiconductor shells2018

    • Author(s)
      Taro Uematsu, Kazutaka Wajima, Dharmendar Kumar Sharma, Shuzo Hirata, Takahisa Yamamoto, Tatsuya Kameyama, Martin Vacha, Tsukasa Torimoto, and Susumu Kuwabata
    • Journal Title

      NPG Asia Mater.

      Volume: 10 Issue: 8 Pages: 713-726

    • DOI

      10.1038/s41427-018-0067-9

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Intrinsic Analysis of Radiative and Room-Temperature Nonradiative Processes Based on Triplet State Intramolecular Vibrations of Heavy Atom-Free Conjugated Molecules toward Efficient Persistent Room-Temperature Phosphorescence2018

    • Author(s)
      Shuzo Hirata
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 9 Issue: 15 Pages: 4251-4259

    • DOI

      10.1021/acs.jpclett.8b01711

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ultralong-Lived Room Temperature Triplet Excitons: Molecular Persistent Room Temperature Phosphorescence and Nonlinear Optical Characteristics with Continuous Irradiation2018

    • Author(s)
      Shuzo Hirata
    • Journal Title

      Journal of Materials Chemistry

      Volume: 6 Issue: 44 Pages: 11785-11794

    • DOI

      10.1039/c8tc01417e

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Large Refractive Index Variations Induced by Accumulating Triplet Excitons under Photoexcitation at Low Power2018

    • Author(s)
      Tomoe Hori, Kenro Totani, Shuzo Hirata, Toshiyuki Watanabe
    • Journal Title

      Chemical Physics Letters

      Volume: 704 Pages: 5-10

    • DOI

      10.1016/j.cplett.2018.05.029

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] 実験と理論の協働によるπ共役系凝集体における三重項失活メカニズムの考察 第69回高分子討論会 無 平田修造 2020/09/16 21国内会議招待講演 蓄光ナノイメージングを可能にする高輝度残光型室温りん光分子の開発2020

    • Author(s)
      平田修造
    • Organizer
      第69回高分子討論会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 蓄光ナノイメージングを可能にする高輝度残光型室温りん光分子の開発2020

    • Author(s)
      平田修造
    • Organizer
      第69回高分子討論会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] Highly Efficient Persistent Room Temperature Phosphorescence From Heavy Atom Free Molecules Triggered By Hidden Long Phosphorescent Antenna2020

    • Author(s)
      Indranil Bhattacharjee, Shuzo Hirata
    • Organizer
      Web Annual Meeting on Photochemistry 2020
    • Related Report
      2020 Annual Research Report
  • [Presentation] ドナーアクセプター直交型キラル分子を利用した高効率熱活性化遅延蛍光発生要因の考察2020

    • Author(s)
      林希久也、松本有正、平田修造
    • Organizer
      2020年web光化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] The effect of the lowest singlet excited state lifetime on up-conversion emission via stepwise two-photon absorption2020

    • Author(s)
      Kentaro Yomogita, Shuzo Hirata
    • Organizer
      Web Annual Meeting on Photochemistry 2020
    • Related Report
      2020 Annual Research Report
  • [Presentation] 置換基誘起の対称禁制遷移分子を用いた弱連続青色光下での大きな光制限効果2020

    • Author(s)
      釜付卓弥、Bhattacharjee Indranil、平田修造
    • Organizer
      日本化学会第101回春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Intrinsic analysis of transition processes from the lowest excited triplet state of heavy atom-free molecules with persistent room-temperature phosphorescence2020

    • Author(s)
      Shuzo Hirata
    • Organizer
      SPIE Photonics Europe, Digital Forum
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Intrinsic analysis of transition processes from the lowest excited triplet state of heavy atom-free conjugated molecular crystals with persistent room temperature phosphorescence2019

    • Author(s)
      Shuzo Hirata
    • Organizer
      2019 MRS Fall Meeting
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Donor-acceptor molecules showing photon upconversion emission by stepwise two photon absorption2019

    • Author(s)
      YOMOGITA Kentaro, ZHANG Junxiang, MIZUTANI Ryota, VAHCA Martin, KAMADA Kenji, MARDER Seth, HIRATA Shuzo
    • Organizer
      Annual Meeting on Photochemistry 2019
    • Related Report
      2019 Annual Research Report
  • [Presentation] Analysis of Triplet State in Conjugated Molecular Crystals toward Persistent Room Temperature Phosphorescence from Soft Crystals2019

    • Author(s)
      Shuzo Hirata
    • Organizer
      The 2nd International Symposium of Soft Crystals
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Exciton management for unique molecular emission characteristics2019

    • Author(s)
      Shuzo Hirata
    • Organizer
      The 36th International Conference of Photopolymer Science and Technology (ICPST-36)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Molecular Materials with Ultralong-Lived Room Temperature Triplet Excitons2019

    • Author(s)
      Shuzo Hirata
    • Organizer
      2019 International Seminar on Polymer Photochemistry (2019 ISPP)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 分散系および凝集系における重原子フリー分子の三重項励起状態2019

    • Author(s)
      平田修造
    • Organizer
      141 M&BE 新分野開拓研究会「有機半導体制御技術の最新動向~分子配向・電荷・励起子~」
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 高効率分子蓄光に向けた三重項からの輻射と非輻射過程の解析2019

    • Author(s)
      平田修造
    • Organizer
      日本化学会第99回春季年会 特別企画 ルミネッセンス化学アンサンブル:発光の未来を探る
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 遷移双極子が小さい光学活性分子材料:円偏光遅延蛍光と円偏光室温蓄光2019

    • Author(s)
      平田修造
    • Organizer
      千葉大学分子キラリティーセンター定例研究会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 分散系共役分子および凝集系共役分子結晶の室温長寿命三重項励起子のサイエンスと機能2018

    • Author(s)
      平田修造
    • Organizer
      東北大学PHyM若手フォーラム
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Intrinsic analysis of radiative process, intramolecular vibrational room-temperature nonradiative process, and quenching process from triplet state for heavy atom-free conjugated structures2018

    • Author(s)
      Shuzo Hirata
    • Organizer
      Annual Meeting on Photochemistry on 2018
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Intrinsic Analysis between Radiative Process and Room-Temperature Nonradiative Process based on Intramolecular Vibrations from Triplet State of Heavy Atom-free Aromatics toward Efficient Persistent Room-temperature Phosphorescence2018

    • Author(s)
      Shuzo Hirata
    • Organizer
      2018 International Seminar on Advanced Materials Research 2018 ISAMR
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Book] 化学工業6月号2021

    • Author(s)
      平田修造
    • Total Pages
      6
    • Publisher
      株式会社化学工業社
    • Related Report
      2020 Annual Research Report
  • [Book] Single-Molecule Level Study and Control of Collective Photosynergetic Responses in Molecules and Molecular Aggregates; Photoresponse in Molecular Complexes and Related Systems2020

    • Author(s)
      Martin Vacha, Shuzo Hirata
    • Total Pages
      21
    • Publisher
      Springer, Singapore
    • ISBN
      9789811554513
    • Related Report
      2020 Annual Research Report
  • [Book] コンバーテック12月号:明るい環境下でも視認可能な高輝度蓄光分子2020

    • Author(s)
      平田修造
    • Total Pages
      4
    • Publisher
      株式会社加工技術研究会
    • Related Report
      2020 Annual Research Report
  • [Book] OPTRONICS11月号2020

    • Author(s)
      平田修造
    • Total Pages
      6
    • Publisher
      株式会社オプトロニクス社
    • Related Report
      2020 Annual Research Report
  • [Book] 環状高分子の合成と機能発現2018

    • Author(s)
      平田修造、バッハマーティン
    • Total Pages
      9
    • Publisher
      シーエムシー出版
    • ISBN
      9784781313993
    • Related Report
      2018 Annual Research Report
  • [Patent(Industrial Property Rights)] 発光材料、及び蓄光材料2020

    • Inventor(s)
      平田修造、バタチャージーインドラニル
    • Industrial Property Rights Holder
      平田修造、バタチャージーインドラニル
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2020 Annual Research Report
  • [Patent(Industrial Property Rights)] 発光材料、及び蓄光材料2020

    • Inventor(s)
      平田 修造 , バタチャージー インドラニル
    • Industrial Property Rights Holder
      平田 修造 , バタチャージー インドラニル
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2020-078341
    • Filing Date
      2020
    • Related Report
      2019 Annual Research Report

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Published: 2018-04-23   Modified: 2022-01-27  

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