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Synthesis and properties of chiral topological molecules with remarkable circular polarlized luminescence

Research Project

Project/Area Number 21K05043
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
Research InstitutionKitasato University

Principal Investigator

Hasegawa Masashi  北里大学, 理学部, 教授 (20438120)

Co-Investigator(Kenkyū-buntansha) 伊與田 正彦  東京都立大学, 理学研究科, 客員教授 (50115995)
Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2023: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2022: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2021: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords円偏光発光 / キラル化合物 / 円二色性スペクトル / 大環状化合物 / 円二色性 / キラル分子 / π共役系化合物 / ヘリセン / ビナフチル / CDスペクトル / ねじれ化合物 / 円偏光発光スペクトル / 蛍光材料 / らせん
Outline of Research at the Start

キラルな分子から生じる円偏光発光(Circularly Polarized Luminescence: CPL)は、偏光を発する光源として三次元表示ディスプレイや情報通信技術に期待されている。しかしながら、どのような分子設計で、どのように発色団を配置すれば高輝度な円偏光源が得られるのか?については不明瞭なままである。本研究では、近接したパイ共役系発色団を対称的に配置し、非局在化した励起状態を導く分子設計により、傑出した円偏光度(gCPL)を持つ材料を創出することを目指す。

Outline of Final Research Achievements

We synthesized several extended π-conjugated compounds with axially chiral binaphthyl and planar chiral [2.2]paracyclophane as chiral sources with high symmetry and achieved improved CPL properties. In particular, high glum values were observed for compounds that are expected to have a high symmetric structure even in the excited state. We have also synthesized molecules with high brightness with a view to light-emitting devices using circularly polarized light. Molecules consisting of [5]helicenes linked to binaphthyl were synthesized and the relationship between the structure and chiral optical properties was investigated. The C2 symmetric structure in both the ground and excited states, parallel control of the magnetic and electric transition dipole moments, and a relatively high asymmetry factor (g-value) in CPL were obtained.

Academic Significance and Societal Importance of the Research Achievements

キラルな分子から生じる円偏光発光(CPL)は、偏光を発する光源としてフィルターレスな液晶バックライトや情報通信技術に期待されている。これらキラル光学特性を利用した新しい技術を実現するには、十分な強度をもつCPL発光物質が必要であり、より高い円偏光度を示す材料が求められるが、キラル光学特性を支配する因子は不明瞭な点が多く、適切な分子設計の指針が存在しない。本研究では対称性の高いキラル分子を用いることで、キラル物性の鍵となる磁気および電気遷移双極子モーメントを制御し、優れた特性を導く分子の開発に成功した。これにより、傑出した特性を持つCPL発光物質の開発が加速されるものと思われる。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • Research Products

    (53 results)

All 2024 2023 2022 2021 Other

All Journal Article (11 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 11 results) Presentation (38 results) (of which Int'l Joint Research: 5 results,  Invited: 5 results) Remarks (4 results)

  • [Journal Article] Synthesis and Chiroptical Properties of Radially Extended Carbazole with Chiral [2.2]Paracyclophane Core2024

    • Author(s)
      Hasegawa Masashi、Xiao Wanli、Ishida Yuki、Asahi Kazuyuki、Nishikawa Hiroyuki、Ohno Reo、Hayauchi Daisuke、Hasegawa Miki、Mazaki Yasuhiro
    • Journal Title

      Advanced Functional Materials

      Volume: - Issue: 47 Pages: 2315215-2315215

    • DOI

      10.1002/adfm.202315215

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Chiroptical Properties of Binaphthyl‐Hinged [5]Helicenes2023

    • Author(s)
      Hasegawa Masashi、Nojima Yuki、Nagata Yuya、Usui Kazuteru、Sugiura Ken‐ichi、Mazaki Yasuhiro
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 26 Issue: 36

    • DOI

      10.1002/ejoc.202300656

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stereogenic π-Conjugated Macrocycles: Synthesis, Structure, and Chiroptical Properties Including Circularly Polarized Luminescence2023

    • Author(s)
      Hasegawa Masashi、Mazaki Yasuhiro
    • Journal Title

      Synlett

      Volume: - Issue: 12 Pages: 1361-1374

    • DOI

      10.1055/a-2158-8820

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Substituent effects on helical structures and chiroptical properties of fused anthracenes with bulky phenyl groups2023

    • Author(s)
      Kenta Suzuki, Hiroki Fukuda, Hayato Toda, Yoshitane Imai, Yuki Nojima, Masashi Hasegawa, Eiji Tsurumaki, Shinji Toyota
    • Journal Title

      Tetrahedron

      Volume: 132 Pages: 133243-133243

    • DOI

      10.1016/j.tet.2022.133243

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Double-Helical S,C-Bridged Tetraphenyl-para-Phenylenediamine and Its Persistent Radical Cation2023

    • Author(s)
      K. Harada, C. Hasegawa, T. Matsumoto, H Sugishita, C. Kitamura, S. Higashibayashi, M. Hasegawa, S. Suzuki, S.-i. Kato
    • Journal Title

      Chem. Commun.

      Volume: 59 Issue: 10 Pages: 1301-1304

    • DOI

      10.1039/d2cc06144a

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Aggregation-induced circularly polarized phosphorescence of Pt(II) complexes with and axially chiral BINOL ligand2023

    • Author(s)
      D. Tauchi, T. Koida, Y. Nojima, M. Hasegawa, Y. Mazaki, A. Inagaki, K. Sugiura, Y. Nagaya, K. Tsubaki, T. Shiga, Y. Nagata, H. Nishikawa
    • Journal Title

      Chem. Commun.

      Volume: 59 Issue: 27 Pages: 4004-4007

    • DOI

      10.1039/d2cc06198h

    • Related Report
      2023 Annual Research Report 2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Multiply Twisted Chiral Macrocycles Clamped by Tethered Binaphthyls Exhibiting High Circularly Polarized Luminescence Brightness2022

    • Author(s)
      Hasegawa Masashi、Hasegawa Chika、Nagaya Yuki、Tsubaki Kazunori、Mazaki Yasuhiro
    • Journal Title

      Chemistry - A European Journal

      Volume: 28 Issue: 59

    • DOI

      10.1002/chem.202202218

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Oxidation of an Internal‐Edge‐Substituted [5]Helicene‐Derived Phosphine Synchronously Enhances Circularly Polarized Luminescence2022

    • Author(s)
      Usui Kazuteru、Narita Nozomi、Eto Ryosuke、Suzuki Seika、Yokoo Atsushi、Yamamoto Kosuke、Igawa Kazunobu、Iizuka Naoko、Mimura Yuki、Umeno Tomohiro、Matsumoto Shota、Hasegawa Masashi、Tomooka Katsuhiko、Imai Yoshitane、Karasawa Satoru
    • Journal Title

      Chemistry - A European Journal

      Volume: 28 Issue: 65

    • DOI

      10.1002/chem.202202922

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chalcogenacalix[4]dithienoselenophene: Synthesis and Properties of Cyclic Thio- and Selenoether of Dithienoselenophene2022

    • Author(s)
      Hasegawa Masashi、Takahashi Kazuhiro、Mazaki Yasuhiro
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 95 Issue: 4 Pages: 628-633

    • DOI

      10.1246/bcsj.20220003

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Helical Oligophenylene Linked with [2.2]Paracyclophane: Stereogenic π‐Conjugated Dye for Highly Emissive Chiroptical Properties2021

    • Author(s)
      Hasegawa Masashi、Ishida Yuki、Sasaki Hiroaki、Ishioka Sumire、Usui Kazuteru、Hara Nobuyuki、Kitahara Maho、Imai Yoshitane、Mazaki Yasuhiro
    • Journal Title

      Chemistry ? A European Journal

      Volume: 27 Issue: 65 Pages: 16225-16231

    • DOI

      10.1002/chem.202103158

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Circularly Polarized Luminescence in Chiral π‐Conjugated Macrocycles2021

    • Author(s)
      Hasegawa Masashi、Nojima Yuki、Mazaki Yasuhiro
    • Journal Title

      ChemPhotoChem

      Volume: 5 Issue: 12 Pages: 1042-1058

    • DOI

      10.1002/cptc.202100162

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Presentation] 軸不斉ユニットに組み込まれた環状ヘリカルオリゴチオフェンの合成と性質2024

    • Author(s)
      川島光、長谷川真士、真崎康博
    • Organizer
      日本化学会 第104春季年会(2024)
    • Related Report
      2023 Annual Research Report
  • [Presentation] Synthesis and chiroptical properties of strained paraphenylene anchoring chiral binaphthyl2024

    • Author(s)
      Masashi Hasegawa
    • Organizer
      Pure and Applied Chemistry International Conference 2024
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and properties of helical oligothiophenes anchored to binaphthyl2024

    • Author(s)
      Hikari Kawashima, Masashi Hasegawa, Yasuhiro Mazaki
    • Organizer
      Pure and Applied Chemistry International Conference 2024
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 軸不斉ユニットに組み込まれた環状オリゴチオフェンの合成と性質2023

    • Author(s)
      川島光、長谷川真士、真崎康博
    • Organizer
      第16回有機π電子系シンポジウム
    • Related Report
      2023 Annual Research Report
  • [Presentation] 架橋ビナフチルで挟まれたキラル大環状アセチレン化合物の合成とキラル光学特性2023

    • Author(s)
      大園真誉、長谷川智香、長谷川真士、真崎康博
    • Organizer
      第33回基礎有機化学討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 軸不斉ユニットに組み込まれた環状オリゴチオフェンの合成と性質2023

    • Author(s)
      川島光、長谷川真士、真崎康博
    • Organizer
      第33回基礎有機化学討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] ビナフチルで架橋された高歪み環状パラフェニレンの合成と発光特性の評価2023

    • Author(s)
      肖万里、長谷川真士、真崎康博
    • Organizer
      第33回基礎有機化学討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] キラルなπ共役系化合物による円偏光発光色素の開発2023

    • Author(s)
      長谷川真士
    • Organizer
      相模中央研究所、材料セミナー
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] Binaphthyl-hinged [5]Helicene Exhibiting Intensive Circularly Polarized Luminescence2023

    • Author(s)
      M. Hasegawa
    • Organizer
      International CPL and CPEL Conference 2023 in Osaka, JAPAN
    • Related Report
      2022 Research-status Report
    • Invited
  • [Presentation] Synthesis and chiroptical properties of strained paraphenylene anchoring by chiral binaphthyl2023

    • Author(s)
      W. Xiao, K. Sato, M. Hasegawa, Y. Mazaki
    • Organizer
      International CPL and CPEL Conference 2023 in Osaka, JAPAN
    • Related Report
      2022 Research-status Report
  • [Presentation] Synthesis and Properties of Helical Oligothiophene Anchored to [2.2]Paracyclophane2023

    • Author(s)
      H. Kawashima, Y. Ishida, M. Hasegawa, Y. Mazaki
    • Organizer
      International CPL and CPEL Conference 2023 in Osaka, JAPAN
    • Related Report
      2022 Research-status Report
  • [Presentation] Photophysical properties of polyfluorene thin films chirally doped by cholesterol derivative2023

    • Author(s)
      K. Asashi, M. Hasegawa, Y. Mazaki, H. Nishikawa
    • Organizer
      International CPL and CPEL Conference 2023 in Osaka, JAPAN
    • Related Report
      2022 Research-status Report
  • [Presentation] Synthesis and photophysical properties of zinc(II) mononuclear complex coordinated by axially chiral Schiff-base ligands2023

    • Author(s)
      D. Tauchi, M. Hasegawa, Y. Mazaki, K.-i. Sugiura, H. Nishikawa
    • Organizer
      International CPL and CPEL Conference 2023 in Osaka, JAPAN
    • Related Report
      2022 Research-status Report
  • [Presentation] ビナフチルで連結された環状[5]ヘリセンの合成とキラル光学特性2023

    • Author(s)
      野島 裕騎、長谷川 真士、真崎 康博
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] ポリフルオレン-ペリレンジイミド誘導体混合薄膜の光物性とデバイス化2023

    • Author(s)
      西村悠紀、長谷川真士、真崎康博、西川浩之
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] 軸不斉を有するシッフ塩基型亜鉛(II)単核錯体の合成と光物性2023

    • Author(s)
      田内大喜、長谷川真士、真崎康博、杉浦健一、西川浩之
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] コレステロール誘導体でキラルドープしたポリフルオレン薄膜の光物性2023

    • Author(s)
      朝日宗将、長谷川真士、真崎康博、西川浩之
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] ビピレン不斉プラットフォームを用いた新規蛍光色素の合成とそのキロプティカル特性2023

    • Author(s)
      小林 礼知、上妻春草ロベルト、石田 真敏、長谷川 真士、杉浦 健一
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] 硫黄と炭素で架橋したダブルヘリカル型テトラフェニル-para-フェニレンジアミンおよびそのラジカルカチオンの合成,構造,物性2023

    • Author(s)
      原田佳歩、長谷川智香、松本泰昌、北村千寿、東林修平、長谷川真士、鈴木修一、加藤 真一郎
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] 動的イミン結合を利用したキラルピレノファンの自己組織化と円偏光発光2023

    • Author(s)
      杉山翔一、野島裕騎、長谷川真士、淺見真年、伊藤傑
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] 光学活性イリジウム発光体からの円偏光発光(CPL)および磁気円偏光発光(MCPL)2023

    • Author(s)
      長谷川公紀、原健吾、長谷川真士、八木繁幸、今井喜胤
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2022 Research-status Report
  • [Presentation] 架橋型軸不斉ビナフチルとパラフェニレンから なるπ拡張キラル大環状化合物の合成とキラル光学特性2022

    • Author(s)
      長谷川智香、長谷川真士、真崎康博
    • Organizer
      第82回有機合成化学協会
    • Related Report
      2022 Research-status Report
  • [Presentation] キラルなビナフチルで固定された高歪みパラ フェニレンの合成とキラル光学特性2022

    • Author(s)
      肖万里、長谷川真士、真崎康博
    • Organizer
      第82回有機合成化学協会
    • Related Report
      2022 Research-status Report
  • [Presentation] キラルなビナフチルで固定された高歪みパラフェニレンの合成とキラル光学特性2022

    • Author(s)
      肖万里、佐藤賢太、長谷川真士、真崎康博
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] 架橋型軸不斉ビナフチルからなるπ拡張キラル大環状化合物の合成とキラル光学特性2022

    • Author(s)
      長谷川智香、長谷川真士、真崎康博
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] ペリレンを有する軸不斉化合物の合成研究2022

    • Author(s)
      小林礼知、藤巻圭介、石田真敏、長谷川真士、真崎康博、杉浦健一
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] 大環状π拡張-3,4-ジフェニルチオフェン6量体の結晶多形挙動2022

    • Author(s)
      渡部裕太、大谷裕之、長谷川真士、 青栁忍、伊與田正彦
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] 二重らせん構造を持つ環状ナフタレン化合物の合成と性質2022

    • Author(s)
      野島裕騎、長谷川真士、真崎康博
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Research-status Report
  • [Presentation] キラルなビナフチルで固定された高歪みパラフェニレンの合成とキラル光学特性2022

    • Author(s)
      肖万里、佐藤賢太、長谷川真士、真崎康博
    • Organizer
      第15回有機π電子系シンポジウム
    • Related Report
      2022 Research-status Report
  • [Presentation] 励起波長依存発光を示すキラルピレノファンの合成と円偏光発光特性2022

    • Author(s)
      杉山翔一、野島裕騎、長谷川真士、淺見真年、伊藤傑
    • Organizer
      第15回有機π電子系シンポジウム
    • Related Report
      2022 Research-status Report
  • [Presentation] キラルなビナフチルで連結された環状[5]ヘリセンの合成と光学的性質、第15回有機π電子系シンポジウム2022

    • Author(s)
      野島裕騎、長谷川真士、真崎康博
    • Organizer
      第15回有機π電子系シンポジウム
    • Related Report
      2022 Research-status Report
  • [Presentation] Synthesis and Properties of Thiacalix[n]thiophene and Its Derivatives2022

    • Author(s)
      M. Hasegawa
    • Organizer
      7th International Symposium of Quantum Beam Science at Ibaraki University
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ビナフチルで固定された 高歪み環状パラフェニレンの合成と発光特性の評価2021

    • Author(s)
      肖万里、長谷川真士、真崎康博
    • Organizer
      日本化学会第102春季年会(2022)
    • Related Report
      2021 Research-status Report
  • [Presentation] 嵩高い置換基をもつチアカリックス[4]ジチエノチオフェン誘導体の合成と機能2021

    • Author(s)
      長谷川真士、廣川巧、加藤南、真崎康博
    • Organizer
      日本化学会第102春季年会(2022)
    • Related Report
      2021 Research-status Report
  • [Presentation] 二重にねじれた環状ナフタレン化合物の合成と性質2021

    • Author(s)
      野島裕騎、長谷川真士、真崎康博
    • Organizer
      日本化学会第102春季年会(2022)
    • Related Report
      2021 Research-status Report
  • [Presentation] キラリティーと磁場の相乗効果によるイリジウム発光体からの革新的円偏光発光(CPL)2021

    • Author(s)
      長谷川公紀、松平華奈、原健吾、森本あみ、長谷川真士、八木繁幸、今井喜胤
    • Organizer
      日本化学会第102春季年会(2022)
    • Related Report
      2021 Research-status Report
  • [Presentation] Circularly Polarized Luminescence of Streogenic Curved Praphenylenes Anchoring A Chiral Binaphthyl2021

    • Author(s)
      Masashi Hasegawa
    • Organizer
      International CREST-CPL Conference 2022 in Awaji, JAPAN
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and Chiroptical Properties of π-Extended Chiral Macrocycles Based on Tethered Binaphthyls2021

    • Author(s)
      Chika Hasegawa, Masashi Hasegawa, Yasuhiro Mzaki
    • Organizer
      International CREST-CPL Conference 2022 in Awaji, JAPAN
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Remarks] 北里大学理学部化学科分子機能化学講座業績ページ

    • URL

      https://www.kitasato-u.ac.jp/sci/research/faculty/performance/?lab_pk=1694482596#content

    • Related Report
      2023 Annual Research Report
  • [Remarks] プレスリリース「高効率の円偏光発光フィルムを生み出すキラル誘起添加剤を開発」

    • URL

      https://www.kitasato.ac.jp/jp/news/20240222-01.html

    • Related Report
      2023 Annual Research Report
  • [Remarks] 北里大学理学部化学科分子機能化学講座のWebサイト

    • URL

      https://www.kitasato-u.ac.jp/sci/resea/kagaku/HP_kinou/Index.html

    • Related Report
      2022 Research-status Report
  • [Remarks] 北里大学理学部化学科分子機能化学講座Webサイト

    • URL

      https://www.kitasato-u.ac.jp/sci/resea/kagaku/HP_kinou/Index.html

    • Related Report
      2021 Research-status Report

URL: 

Published: 2021-04-28   Modified: 2025-01-30  

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