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2018 Fiscal Year Annual Research Report

Emerging CPL-active polymers by wavelength-selective CP light source

Research Project

Project/Area Number 16H04155
Research InstitutionNara Institute of Science and Technology

Principal Investigator

藤木 道也  奈良先端科学技術大学院大学, 先端科学技術研究科, 教授 (00346313)

Project Period (FY) 2016-04-01 – 2019-03-31
Keywords円偏光発光 / 円二色性 / Cryprochiralit
Outline of Annual Research Achievements

近年円偏光発光(CPL)性機能材料の研究が活発である。発光性高分子、分子、金属錯体は、基底状態(S0)の不斉構造に由来する円二色性(CD)を、励起状態(S1)の不斉構造に由来するCPL特性を示す。CD/CPL特性の付与には化学的不斉源を用いるため、CPL信号の発生・消去・符号反転・固定の可逆な制御は困難である。物理バイアス(光、電場、磁場)であればこれらの特性制御が可能になる。本研究では円偏光源によるCPL信号の保持と反転を含むCPL信号誘起/消去/反転/固定を完全制御するため、基底状態(S0)では2-3kcal/mol(単結合当り)程度の回転障壁を持ち、CD不活性な蛍光性高分子や蛍光性オリゴマーを用い、円偏光源の波長選択により10^-15秒で励起状態(S1, S2...)にしたのち、回転・振動モード(10^-15秒)によりCPL信号が最大になる最低振動励起準位(S1(v'=0))に落ち込み、左右にねじれた準安定構造(寿命:10^-8秒)となり、S0(v=0,1,2)状態ヘ緩和してCPL発光する機構を考案した。
1. 基底状態と励起状態の不斉構造は同一とは限らず、逆転、あるいは常に同一の負符号のみを示す現象を見出した。
2. 円偏光源の励起波長によって非フォトクロミックの高分子、オリゴマー、低分子にも不斉性が誘起され、その左右性が励起波長で支配されるとの一般性を実証した。
3. Mislowが提唱したCryprochiralityの概念を証明するため、近畿大学グループと共同で、基底状態ではCD不活性だが励起状態ではCPL活性な不斉分子系をいくつか見出した。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

  • Research Products

    (26 results)

All 2019 2018 Other

All Int'l Joint Research (3 results) Journal Article (15 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 15 results,  Open Access: 5 results) Presentation (7 results) (of which Int'l Joint Research: 2 results,  Invited: 4 results) Remarks (1 results)

  • [Int'l Joint Research] 蘇州大学/中国科学技術大学/東北林業大学(中国)

    • Country Name
      CHINA
    • Counterpart Institution
      蘇州大学/中国科学技術大学/東北林業大学
  • [Int'l Joint Research] Universiti Malaysia Perlis(マレーシア)

    • Country Name
      MALAYSIA
    • Counterpart Institution
      Universiti Malaysia Perlis
  • [Int'l Joint Research] Universite Libre de Bruxelles(ベルギー)

    • Country Name
      BELGIUM
    • Counterpart Institution
      Universite Libre de Bruxelles
  • [Journal Article] Photoluminescent poly(4-vinylpyridine)-based ionic liquids coded with l- and d-histidine: a supramolecular self-assembly leading to the formation of red-shifted photoluminescent helical aggregates2019

    • Author(s)
      Puneet Puhup、Horechyy Andriy、Srivastava Rajiiv K.、Nandan Bhanu、Fujiki Michiya
    • Journal Title

      Polymer Chemistry

      Volume: 10 Pages: -

    • DOI

      10.1039/C9PY00181F

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Questions of Mirror Symmetry at the Photoexcited and Ground States of Non-Rigid Luminophores Raised by Circularly Polarized Luminescence and Circular Dichroism Spectroscopy. Part 2. Perylenes, BODIPYs, Molecular Scintillators, Coumarins, Rhodamine B, and DCM2019

    • Author(s)
      Michiya Fujiki, Julian R. Koe, Seiko Amazumi
    • Journal Title

      Symmetry

      Volume: 13 Pages: 363

    • DOI

      10.3390/sym11030363

    • Peer Reviewed / Open Access
  • [Journal Article] Aggregation-induced chiroptical generation and photoinduced switching of achiral azobenzene-alt-fluorene copolymer endowed with left- and right-handed helical polysilanes2019

    • Author(s)
      Chen, Hailing, Yin, Lu, Liu, Meng, Wang, Laibing, Fujiki, Michiya, Zhang, Wei, Zhu, Xiulin
    • Journal Title

      RSC Advances

      Volume: 9 Pages: 4849-4853

    • DOI

      10.1039/C8RA09345H

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] The Chirality Induction and Modulation of Polymers by Circularly Polarized Light2019

    • Author(s)
      Yang Guang, Zhang Siyu, Hu Jingan, Fujiki Michiy, Zou Gang
    • Journal Title

      Symmetry

      Volume: 11 Pages: 474-474

    • DOI

      10.3390/sym11040474

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Synthesis of delayed-emissive poly (2, 7-carbazole) s having an anchored triazine pendant at N-position2019

    • Author(s)
      Fumihiro Aso, Hidehisa Kawashima, Michiya Fujiki, Masashi Kijima
    • Journal Title

      Polymer Chemistry

      Volume: 10 Pages: -

    • DOI

      10.1039/C9PY00152B

    • Peer Reviewed
  • [Journal Article] Questions of Mirror Symmetry at the Photoexcited and Ground States of Non-Rigid Luminophores Raised by Circularly Polarized Luminescence and Circular Dichroism Spectroscopy: Part 1. Oligofluorenes, Oligophenylenes, Binaphthyls and Fused Aromatics2018

    • Author(s)
      Michiya Fujiki, Julian R. Koe, Takashi Mori, Yoshihiro Kimura
    • Journal Title

      Molecules

      Volume: 23 Pages: 2606

    • DOI

      10.3390/molecules23102606

    • Peer Reviewed / Open Access
  • [Journal Article] A Combined Experimental and Theoretical Study on Circular Dichroism and Circularly Polarized Luminescence of Configurationally Robust Symmetric Triple Pentahelicene2018

    • Author(s)
      Tanaka Hiroki, Kato Yuka, Fujiki Michiya, Inoue Yoshihisa, Mori Tadashi
    • Journal Title

      Journal of Physical Chemistry A

      Volume: 122 Pages: 7378-7384

    • DOI

      10.1021/acs.jpca.8b05247

    • Peer Reviewed
  • [Journal Article] A Pivotal Biaryl Rotamer Bearing Two Floppy Pyrenes that Exhibits Cryptochiral Characteristics in the Ground State2018

    • Author(s)
      Nobuyuki Hara, Masaki Yanai, Daiki Kaji, Motohiro Shizuma, Nobuo Tajima, Michiya Fujiki, Yoshitane Imai
    • Journal Title

      ChemistrySelect

      Volume: 3 Pages: 9970-9973

    • DOI

      10.1002/slct.201801770

    • Peer Reviewed
  • [Journal Article] Unveiling controlled breaking of the mirror symmetry of Eu(fod)3 with α-/β-pinene and BINAP by circularly polarised luminescence (CPL), CPL excitation, and 19F-/31P{1H}-NMR spectra and Mulliken charges2018

    • Author(s)
      Abd Jalil Jalilah Fumio Asanoma, Michiya Fujiki
    • Journal Title

      Inorganic Chemistry Frontiers

      Volume: 5 Pages: 2718-2733

    • DOI

      10.1039/C8QI00509E

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Optically Active Linear and Hyperbranched Polythiophenes Bearing BINOL Derivatives Emitting Circularly Polarized Luminescence2018

    • Author(s)
      Nobuyuki Hara, Mamoru Okazaki, Takuma Kitatobe, Nobuo Tajima, Motohiro Shizuma, Atsushi Sudo, Hisashi Fujihara, Michiya Fujiki, Yoshitane, Imai
    • Journal Title

      Chemistry Letters

      Volume: 47 Pages: 2718-2733

    • DOI

      10.1246/cl.180536

    • Peer Reviewed
  • [Journal Article] Symmetry-based rational design for boosting chiroptical responses2018

    • Author(s)
      Hiroki Tanaka, Mina Ikenosako, Yuka Kato, Michiya Fujiki, Yoshihisa Inoue, Tadashi Mori
    • Journal Title

      Communications Chemistry

      Volume: 1 Pages: 38

    • DOI

      10.1038/s42004-018-0035-x

    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis and Optical Properties in Terthiophene Functionalized Conjugated Triarm Polymers Containing Poly(fluorene-2,7-vinylene) Arms Having Different Cores2018

    • Author(s)
      Kotohiro Nomura, Tomohiro Miwata, Takuya Shinozuka, Munetsugu Morita, Yves H. Geerts, Michiya Fujiki, Motoko S. Asano
    • Journal Title

      ACS Omega

      Volume: 3 Pages: 5052-5063

    • DOI

      10.1021/acsomega.8b00676

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Molecular weight dependent physisorption of non-charged poly(dioctylfluorene) onto the neutral surface of cuboidal γ-alumina in toluene2018

    • Author(s)
      Kazuki Yamazaki, Ayako Nakao, Nozomu Suzuki, Michiya Fujiki
    • Journal Title

      Polymer Journal

      Volume: 50 Pages: 865-877

    • DOI

      10.1038/s41428-018-0046-6

    • Peer Reviewed
  • [Journal Article] Noticeable Chiral Center Dependence of Signs and Magnitudes in Circular Dichroism (CD) and Circularly Polarized Luminescence (CPL) Spectra of All-trans Poly(9,9-dialkyl-fluorene-2,7-vinylene)s Bearing Chiral Alkyl Side Chains in Solution, Aggregates, and in Thin Films2018

    • Author(s)
      Takumi Yamada, Kotohiro Nomura, Michiya Fujiki
    • Journal Title

      Macromolecules

      Volume: 51 Pages: 2377-2387

    • DOI

      10.1021/acs.macromol.8b00241

    • Peer Reviewed
  • [Journal Article] Turn-on circularly polarized luminescent (CPL) molecular system realized by thermo-driven Newman-Kwart rearrangement reaction from CPL-silent O- to CPL-active S-thiocarbamate groups at peripheral position of 1,1'-binapthyl rings2018

    • Author(s)
      Takuya Sato, Nobuyuki Hara, Nobuo Tajima, Atsushi Sudo, Michiya Fujiki, Yoshitane Imai
    • Journal Title

      Tetrahedron Letters

      Volume: 59 Pages: 1619-1622

    • DOI

      10.1016/j.tetlet.2018.03.001

    • Peer Reviewed
  • [Presentation] 円偏光・光渦による分子不斉の発生と制御:現状と展望2018

    • Author(s)
      藤木道也
    • Organizer
      自然科学研究機構分野融合型共同研究事業「光渦が拓く新しい自然科学」研究会「光・物質・生命におけるキラリティ
    • Invited
  • [Presentation] Controlled mirror symmetry breaking, restoration, inversion, and memory in polymers, molecules, and lanthanide complexes by CD-and-CPL spectroscopy2018

    • Author(s)
      Michiya Fujiki
    • Organizer
      International Congress on Pure & Applied Chemistry Langkawi
    • Int'l Joint Research / Invited
  • [Presentation] 可溶性セルロース誘導体から光学不活性発光体への分子間不斉転写法による円偏光発光吸収特性の付与2018

    • Author(s)
      藤木 道也、Guo Sibo, 鈴木 望、Wang Leibing、大久保 明日香、上手 大暉
    • Organizer
      第67回高分子討論会(2018年9月12日-14日, 北海道大学)
  • [Presentation] Cellulose Chirality Transfer to Luminescent Polymers, Molecules and Metal Complexes:  Importance of intermolecular CH/O, CH/π, CH/F and π/π Interactions2018

    • Author(s)
      Michiya Fujiki
    • Organizer
      4th Molecular Chirality Asia 2018
    • Int'l Joint Research / Invited
  • [Presentation] 非古典的アプローチによる不斉高分子と不斉分子の発生と制御 : CD/CPL/CPLE分光法と計算化学的手法を組み合わせて2018

    • Author(s)
      藤木 道也
    • Organizer
      2018年モレキュラーキラリティーシンポジウム
    • Invited
  • [Presentation] 光学活性ビナフチルを基軸とするソルバトクロミック円偏光発光(CPL)体の創製2018

    • Author(s)
      原 伸行,奥田 晃史,靜間 基博,藤木 道也,今井 喜胤
    • Organizer
      2018年モレキュラーキラリティーシンポジウム
  • [Presentation] 光学活性カルボン酸/メタルハイブリッド発光体の創製と円偏光発光(CPL)特性2018

    • Author(s)
      原 伸行,楫 大輝,靜間 基博,藤木 道也,今井 喜胤
    • Organizer
      2018年モレキュラーキラリティーシンポジウム
  • [Remarks] NAIST 高分子創成科学研究室

    • URL

      http://mswebs.naist.jp/LABs/fujiki/index.html

URL: 

Published: 2019-12-27  

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