Creation of Photoresponsive Organic Ferroelectrics with Strong Correlation between Proton Transfer and Photoisomerization Reactions

• Project Area: Science on Function of Soft Molecular Systems by Cooperation of Theory and Experiment
• Project/Area Number: 16H00851
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Rikkyo University
• Principal Investigator: 森本 正和 立教大学, 理学部, 教授 (70447126)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000); Fiscal Year 2017: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000); Fiscal Year 2016: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 超分子化学 / 分子性固体 / 誘電体物性 / フォトクロミズム / 水素結合

Outline of Annual Research Achievements

外部刺激に柔軟に応答する柔らかな分子系における新現象・新機能の発掘に関する研究として、フォトクロミック分子の光異性化反応により強誘電物性を可逆的に変化させる有機分子結晶を創出することを目的とした。分子間プロトン移動機構により強誘電性を発現し得る水素結合性フォトクロミック分子結晶を合成し、それらの結晶相光反応、ならびに結晶構造と誘電物性との関係について検討した。
水素結合性のイミダゾールを有する様々なフォトクロミック分子を合成した。これらの分子結晶の多くは紫外光と可視光の照射により可逆的な光異性化反応を起こし、フォトクロミズムを示した。その一部の誘導体の結晶において、一次元水素結合ネットワークに関与するイミダゾールのN-H水素原子がディスオーダーしていた。これは、互いに等価であるがN-H水素原子の配向の異なる水素結合構造が結晶中において混在しているためと考えられる。この単結晶の電気物性を測定したところ、分子間プロトン移動に由来すると考えられる誘電率の温度依存性・電場周波数依存性が観測された。水素原子のディスオーダーと誘電応答の有無は、結晶構造の対称性に依存することが分かった。100～300 Kにおいて分極-電場ヒステリシスを測定したが、ヒステリシスループの開きは観測されず、この単結晶について強誘電性の発現は認められなかった。強誘電性の発現のためには、結晶中での水素結合一次元鎖同士を接近させることで鎖間の電気的相関を強くするなどの結晶構造設計が必要と考えている。本研究で設計・合成した水素結合性フォトクロミック分子を用いることで、プロトン移動に由来する誘電応答と光化学反応性とを併せもつ複合機能有機分子結晶を構築できることが分かった。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] A turn-on mode fluorescent diarylethene: Solvatochromism of fluorescence (2018)
  • Author(s): Masakazu Morimoto, Yuta Takagi, Karina Hioki, Tatsuhiro Nagasaka, Hikaru Sotome, Syoji Ito, Hiroshi Miyasaka, Masahiro Irie
  • Journal Title: Dyes and Pigments Volume: 153 Pages: 144-149
  • DOI: 10.1016/j.dyepig.2018.02.016
  • Peer Reviewed
• [Journal Article] Photoswitchable Turn-on Mode Fluorescent Diarylethenes: Strategies for Controlling the Switching Response (2018)
  • Author(s): Masahiro Irie, Masakazu Morimoto
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 91 Issue: 2 Pages: 237-250
  • DOI: 10.1246/bcsj.20170365
  • NAID: 130006350252
  • Peer Reviewed / Open Access
• [Journal Article] Fluorescence Photoswitching of a Diarylethene by Irradiation with Single-Wavelength Visible Light (2017)
  • Author(s): Ryota Kashihara, Masakazu Morimoto, Syoji Ito, Hiroshi Miyasaka, Masahiro Irie
  • Journal Title: Journal of the American Chemical Society Volume: 139 Issue: 46 Pages: 16498-16501
  • DOI: 10.1021/jacs.7b10697
  • Peer Reviewed
• [Journal Article] Thermal decomposition product of 1,2-bis(2-methyl-1-benzofuran-3-yl)perfluorocyclopentene (2017)
  • Author(s): T. Yamaguchi, T. Nakagawa, T. Ozeki, M. Fukuda, M. Morimoto, S. Takami
  • Journal Title: Tetrahedron Letters Volume: 58 Issue: 47 Pages: 4447-4449
  • DOI: 10.1016/j.tetlet.2017.10.017
  • Peer Reviewed
• [Journal Article] Photosalient Phenomena that Mimic Impatiens Are Observed in Hollow Crystals of Diarylethene with a Perfluorocyclohexene Ring (2017)
  • Author(s): Eri Hatano, Masakazu Morimoto, Takahito Imai, Kengo Hyodo, Ayako Fujimoto, Ryo Nishimura, Akiko Sekine, Nobuhiro Yasuda, Satoshi Yokojima, Shinichiro Nakamura, Kingo Uchida
  • Journal Title: Angewandte Chemie International Edition Volume: 56 Issue: 41 Pages: 12576-12580
  • DOI: 10.1002/anie.201706684
  • Peer Reviewed
• [Journal Article] Photoswitchable Fluorescent Diarylethene Derivatives with Thiophene 1,1-Dioxide Groups: Effect of Alkyl Substituents at the Reactive Carbons (2017)
  • Author(s): Masakazu Morimoto, Takaki Sumi, Masahiro Irie
  • Journal Title: Materials Volume: 10 Issue: 9 Pages: 1021-1021
  • DOI: 10.3390/ma10091021
  • Peer Reviewed / Open Access
• [Journal Article] Photoregulation of Retro-Diels-Alder Reaction at the Center of Polymer Chains (2017)
  • Author(s): Jumpei Kida, Keiichi Imato, Raita Goseki, Masakazu Morimoto, Hideyuki Otsuka
  • Journal Title: Chemistry Letters Volume: 46 Issue: 7 Pages: 992-994
  • DOI: 10.1246/cl.170251
  • NAID: 130005709480
  • Peer Reviewed
• [Journal Article] Diastereoselective photocyclization of a photochromic diarylethene having a benzo[b]phosphole P-oxide group (2017)
  • Author(s): Tomohiro Ichikawa, Masakazu Morimoto, Masahiro Irie
  • Journal Title: Dyes and Pigments Volume: 137 Pages: 214-220
  • DOI: 10.1016/j.dyepig.2016.10.010
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Light-Driven Molecular Crystal Actuators: An Approach to Molecular Machinery (2016)
  • Author(s): 森本正和、入江正浩
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 74 Issue: 12 Pages: 1217-1224
  • DOI: 10.5059/yukigoseikyokaishi.74.1217
  • NAID: 130005251194
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed
• [Journal Article] Turn-on mode fluorescence photoswitching of diarylethene single crystals (2016)
  • Author(s): Masakazu Morimoto, Ryota Kashihara, Katsuya Mutoh, Yoichi Kobayashi, Jiro Abe, Hikaru Sotome, Syoji Ito, Hiroshi Miyasaka, Masahiro Irie
  • Journal Title: CrystEngComm Volume: 18 Issue: 38 Pages: 7241-7248
  • DOI: 10.1039/c6ce00725b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Photoinduced topographical changes on microcrystalline surfaces of diarylethenes (2016)
  • Author(s): Noriko Fujinaga, Naoki Nishikawa, Ryo Nishimura, Kengo Hyodo, Seiji Yamazoe, Yuko Kojima, Kazuki Yamamoto, Tsuyoshi Tsujioka, Masakazu Morimoto, Satoshi Yokojima, Shinichiro Nakamura, Kingo Uchida
  • Journal Title: CrystEngComm Volume: 18 Issue: 38 Pages: 7229-7235
  • DOI: 10.1039/c6ce00718j
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Photosalient effect of a diarylethene with a perfluorocyclohexene ring (2016)
  • Author(s): Eri Hatano, Masakazu Morimoto, Kengo Hyodo, Nobuhiro Yasuda, Satoshi Yokojima, Shinichiro Nakamura, Kingo Uchida
  • Journal Title: Chemistry-A European Journal Volume: 22 Issue: 36 Pages: 12680-12683
  • DOI: 10.1002/chem.201603020
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Emission color tuning and white-light generation based on photochromic control of energy transfer reactions in polymer micelles (2016)
  • Author(s): Magnus Balter, Shiming Li, Masakazu Morimoto, Sicheng Tang, Jordi Hernando, Gonzalo Guirado, Masahiro Irie, Francisco M. Raymo, Joakim Andreasson
  • Journal Title: Chemical Science Volume: 7 Issue: 9 Pages: 5867-5871
  • DOI: 10.1039/c6sc01623e
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photoinduced reversible formation of a superhydrophilic surface by crystal growth of diarylethene (2016)
  • Author(s): Kazuki Takase, Kengo Hyodo, Masakazu Morimoto, Yuko Kojima, Hiroyuki Mayama, Satoshi Yokojima, Shinichiro Nakamura and Kingo Uchida
  • Journal Title: Chemical Communications Volume: 52 Issue: 42 Pages: 6885-6887
  • DOI: 10.1039/c6cc01638c
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] 1D chains of lanthanoid ions and a dithienylethene ligand showing slow relaxation of the magnetization (2016)
  • Author(s): Mudasir Ahmad Yatoo, Goulven Cosquer, Masakazu Morimoto, Masahiro Irie, Brian K. Breedlove, Masahiro Yamashita
  • Journal Title: Magnetochemistry Volume: 2 Issue: 2 Pages: 21-21
  • DOI: 10.3390/magnetochemistry2020021
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photo-activation of single molecule magnet behavior in a manganese-based complex (2016)
  • Author(s): Ahmed Fetoh, Goulven Cosquer, Masakazu Morimoto, Masahiro Irie, Ola El-Gammal, Gaber Abu El-Reash, Brian K. Breedlove, Masahiro Yamashita
  • Journal Title: Scientific Reports Volume: 6 Issue: 1
  • DOI: 10.1038/srep23785
  • Peer Reviewed / Open Access
• [Presentation] Photomechanical Performance of Diarylethene Single Crystals (2017)
  • Author(s): Masakazu Morimoto
  • Organizer: 日本化学会第97春季年会 Asian International Symposium -Organic Crystals-
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県横浜市港北区日吉）
  • Year and Date: 2017-03-16
  • Int'l Joint Research / Invited
• [Presentation] Photochromism and mechanical performance of diarylethene single crystals (2017)
  • Author(s): Masakazu Morimoto
  • Organizer: The 39th Progress In Electromagnetics Research Symposium
  • Int'l Joint Research / Invited
• [Presentation] フォトクロミック分子・分子結晶の光反応と物性 (2017)
  • Author(s): 森本正和
  • Organizer: 日本物理学会2017年秋季大会
  • Invited
• [Presentation] Turn-on mode fluorescence photoswitching of diarylethene single crystals (2016)
  • Author(s): Masakazu Morimoto, Ryota Kashihara, Katsuya Mutoh, Yoichi Kobayashi, Jiro Abe, Hikaru Sotome, Syoji Ito, Hiroshi Miyasaka, Masahiro Irie
  • Organizer: International Symposium on Photochromism 2016 (ISOP 2016)
  • Place of Presentation: East China University of Science and Technology (ECUST), Shanghai, China
  • Year and Date: 2016-11-04
  • Int'l Joint Research
• [Presentation] ベンゾホスホール基を有するジアリールエテンの不斉光反応 (2016)
  • Author(s): 市川智浩、森本正和、入江正浩
  • Organizer: 2016年光化学討論会
  • Place of Presentation: 東京大学駒場第一キャンパス（東京都目黒区駒場）
  • Year and Date: 2016-09-06
• [Remarks] 立教大学森本正和研究室ホームページ
  • URL: http://www2.rikkyo.ac.jp/web/m-morimoto/index.html
• [Remarks] 立教大学森本研究室ホームページ
  • URL: http://www2.rikkyo.ac.jp/web/m-morimoto/index.html