Photo-thermal Energy Conversion Based on Photo-Electrochromic Molecules

• Project/Area Number: 18H03919
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 35:Polymers, organic materials, and related fields
• Research Institution: Nara Institute of Science and Technology
• Principal Investigator: KAWAI TSUYOSHI 奈良先端科学技術大学院大学, 先端科学技術研究科, 教授 (40221197)
• Co-Investigator(Kenkyū-buntansha): 東田 卓 大阪公立大学工業高等専門学校, その他部局等, 教授 (00208745)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥43,680,000 (Direct Cost: ¥33,600,000、Indirect Cost: ¥10,080,000); Fiscal Year 2021: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000); Fiscal Year 2020: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000); Fiscal Year 2019: ¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000); Fiscal Year 2018: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000)
• Keywords: 光エネルギー変換 / フォトクロミズム / 光異性化 / エンタルピー変化 / 内部エンタルピー / 異性化 / 光反応量子収率 / エネルギー貯蔵 / 太陽エネルギー / 連鎖反応 / フォトクロミック分子 / 光反応分子 / 光熱エネルギー貯蔵 / 光反応 / エンタルピー / 量子収率

Outline of Final Research Achievements

Photoelectrochromic molecules having efficient light-heat energy storage molecules were studied. Photocxhromic molecules store a part of light energy upon photoisomerization and can be released out at reverse photo- or electro-isomerization. Some of terarylene-type photoelectrochromic molecules actually displayed efficient photothermal energy storage capability with significant energy storage capacity and large energy release upon electro-induced chain isomerization reaction.

Academic Significance and Societal Importance of the Research Achievements

光異性化反応に伴う内部エネルギーの貯蔵容量が大きい分子は、光異性化に伴うエンタルピー変化が大きく、いわゆる線形自由エネルギー変化則（LFER則）から逆異性化反応における活性化エネルギーが小さく高エネルギー状態の保存性が低くなる。すなわちエネルギー保持容量と保持安定性とはトレードオフとなる。本研究では、系統的な検討を行い単純な置換基効果では、LFERに伴うエネルギー保持における安定性と保持容量の両立が難しいことを示したうえで、芳香族ユニットを変えることで両者の両立が可能となることを見出し、新しい高熱変換貯蔵材料の分子設計指針を明らかにした。

Research Products

• [Int'l Joint Research] ENS-Paris Saclay/Univ Paris-Saclay/Univ Toulouse(フランス)
• [Int'l Joint Research] University of Toulouse/University of Paris Saclay(フランス)
• [Int'l Joint Research] University of Tolouse/University of Paris Saclay(フランス)
• [Int'l Joint Research] University of Toulouse/CEMES-CNRS(フランス)
• [Journal Article] Investigations into oxidation induced ring opening of terarylenes containing π-extended thieno[<i>b</i>]thiophene units (2023)
  • Author(s): Martin Colin J.、Goto Yora、Asato Ryosuke、Rapenne Gwrnael、Kawai Tsuyoshi
  • Journal Title: New Journal of Chemistry Volume: 47 Issue: 6 Pages: 2832-2839
  • DOI: 10.1039/d2nj05726c
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Tetrathienyl Corannulene Compounds with Highly Sensitive Photochromism (2022)
  • Author(s): Yamada Mihoko、Sawazaki Tomoya、Fujita Mae、Asanoma Fumio、Nishikawa Yoshiko、Kawai Tsuyoshi
  • Journal Title: Chemistry - A European Journal Volume: 28 Issue: 49 Pages: 1-8
  • DOI: 10.1002/chem.202201286
  • Peer Reviewed
• [Journal Article] 1,4-Naphthoquinone Derivative as Efficient Photolabile Molecule: Concise Synthesis and Photorelease of Various Functional Compounds (2022)
  • Author(s): Kawai Tsuyoshi、Morimoto Tsumoru、Liu HaiYing、Suzuki Mikiya、Kakiuchi Kiyomi
  • Journal Title: Synthesis Volume: 55 Issue: 01 Pages: 150-158
  • DOI: 10.1055/a-1932-5940
  • Peer Reviewed
• [Journal Article] Photoisomerization of Covalently Attached Diarylethene on Locally Functionalized Single-Walled Carbon Nanotubes for Photoinduced Wavelength Switching of Near-Infrared Photoluminescence (2022)
  • Author(s): Nakagawa Yasuto、Yu Boda、Niidome Yoshiaki、Hayashi Keita、Staykov Aleksandar、Yamada Miku、Nakashima Takuya、Kawai Tsuyoshi、Fujigaya Tsuyohiko、Shiraki Tomohiro
  • Journal Title: The Journal of Physical Chemistry C Volume: 126 Issue: 25 Pages: 10478-10486
  • DOI: 10.1021/acs.jpcc.2c02977
  • Peer Reviewed
• [Journal Article] Molecular Rotor Functionalized with a Photoresponsive Brake (2021)
  • Author(s): Asato Ryosuke、Martin Colin J.、Abid Seifallah、Gisbert Yohan、Asanoma Fumio、Nakashima Takuya、Kammerer Claire、Kawai Tsuyoshi、Rapenne Gwenael
  • Journal Title: Inorganic Chemistry Volume: 60 Issue: 6 Pages: 3492-3501
  • DOI: 10.1021/acs.inorgchem.0c03330
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Systematic studies of structural variations in terarylene photohydride generators (2020)
  • Author(s): Martin Colin J.、Calupitan Jan Patrick、Minamide Miho、Asato Ryosuke、Goto Yora、Rapenne Gwenael、Nakashima Takuya、Kawai Tsuyoshi
  • Journal Title: Journal of Photochemistry and Photobiology A: Chemistry Volume: 397 Pages: 112594-112594
  • DOI: 10.1016/j.jphotochem.2020.112594
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Restriction of the Conrotatory Motion in Photo-Induced 6π Electrocyclic Reaction: Formation of the Excited State of the Closed-Ring Isomer in the Cyclization (2020)
  • Author(s): Tatsuhiro Nagasaka, Hikaru Sotome, Soichiro Morikawa, Lucas Martinez Uriarte, Michel Sliwa, Tsuyoshi Kawai, Hiroshi Miyasaka
  • Journal Title: RSC Adv. Volume: 10 Issue: 34 Pages: 20038-20045
  • DOI: 10.1039/d0ra03523h
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photosynergetic amplification of radiation input: from efficient UV induced cycloreversion to sensitive X-ray detection (2020)
  • Author(s): Asato Ryosuke、Martin Colin J.、Calupitan Jan Patrick、Mizutsu Ryo、Nakashima Takuya、Okada Go、Kawaguchi Noriaki、Yanagida Takayuki、Kawai Tsuyoshi
  • Journal Title: Chemical Science Volume: 11 Issue: 9 Pages: 2504-2510
  • DOI: 10.1039/c9sc05380h
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Aqueous Photon Upconversion by Anionic Acceptors Self-Assembled on Cationic Bilayer Membranes with a Long Triplet Lifetime (2019)
  • Author(s): Asthana Deepak、Hisamitsu Shota、Morikawa Masa-aki、Duan Pengfei、Nakashima Takuya、Kawai Tsuyoshi、Yanai Nobuhiro、Kimizuka Nobuo
  • Journal Title: Organic Materials Volume: 01 Issue: 01 Pages: 043-049
  • DOI: 10.1055/s-0039-3400250
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Photochromic Performance of 5-Heteroaryl-4-vinyl-2-phenylthiazole Derivatives (2019)
  • Author(s): Shizuka Takami, Minori Nishiyama, Masaki Mizuno, Tadatsugu Yamaguchi, Yuichiro Hashimoto, Tsuyoshi Kawai
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 92 Issue: 10 Pages: 1773-1778
  • DOI: 10.1246/bcsj.20190093
  • NAID: 130007728641
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Photochromic diarylethenes designed for surface deposition: from self‐assembled monolayers to single molecules (2019)
  • Author(s): Calupitan Jan Patrick Dela Cruz、Galangau Olivier、Nakashima Takuya、Kawai Tsuyoshi、Rapenne Gwenael
  • Journal Title: ChemPlusChem Volume: 84 Issue: 6 Pages: 564-577
  • DOI: 10.1002/cplu.201800640
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Ligand-to-Ligand Interactions That Direct Formation of D2-Symmetrical Alternating Circular Helicate (2018)
  • Author(s): Bing Tan Yan、Kawai Tsuyoshi、Yuasa Junpei
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 10 Pages: 3683-3689
  • DOI: 10.1021/jacs.7b12663
  • Peer Reviewed
• [Journal Article] Adsorption of Terarylenes on Ag(111) and NaCl(001)/Ag(111): A Scanning Tunneling Microscopy and Density Functional Theory Study (2018)
  • Author(s): Calupitan Jan Patrick Dela Cruz、Guillermet Olivier、Galangau Olivier、Yengui Mayssa、Echeverria Jorge、Bouju Xavier、Nakashima Takuya、Rapenne Gwenael 、Coratger Roland、Kawai Tsuyoshi
  • Journal Title: The Journal of Physical Chemistry C Volume: 122 Issue: 11 Pages: 5978-5991
  • DOI: 10.1021/acs.jpcc.7b11122
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Circularly Polarized Luminescence from Inorganic Materials-Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts (2018)
  • Author(s): M. Sugimoto, X.-L. Liu, S. Tsunega, E. Nakajima, S. Abe, T. Nakashima, T. Kawai, R.-H. Jin
  • Journal Title: Chem. Eur. J. Volume: 24 Issue: 25 Pages: 6519-6524
  • DOI: 10.1002/chem.201705862
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Hierarchical Emergence and Dynamic Control of Chirality in a Photoresponsive Dinuclear Complex (2018)
  • Author(s): Hashimoto Yuichiro、Nakashima Takuya、Yamada Miku、Yuasa Jupnei、Rapenne Gwenael、Kawai Tsuyoshi
  • Journal Title: J. Phys. Chem. Lett. Volume: 9 Issue: 9 Pages: 2151-2157
  • DOI: 10.1021/acs.jpclett.8b00690
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Dynamic Modulation of Circularly Polarized Luminescence in Photoresponsive Assemblies (2018)
  • Author(s): Hashimoto Yuichiro、Nakashima Takuya、Kuno Jumpei、Yamada Miku、Kawai Tsuyoshi
  • Journal Title: ChemNanoMat Volume: 4 Issue: 8 Pages: 815-820
  • DOI: 10.1002/cnma.201800124
  • Peer Reviewed
• [Journal Article] Impact of Optical Purity on the Light Harvesting Property in Supramolecular Nanofibers (2018)
  • Author(s): Ramarani Sethy, Remi Metivier, Arnaud Brosseau, Tsuyoshi Kawai, Takuya Nakashima
  • Journal Title: J. Phys. Chem. Lett. Volume: 9 Issue: 16 Pages: 4516-5421
  • DOI: 10.1021/acs.jpclett.8b02015
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Terarylenes as Photoactivatable Hydride Donors (2018)
  • Author(s): Martin Colin J.、Minamide Miho、Dela Cruz Calupitan Jan Patrick、Asato Ryosuke、Kuno Jumpei、Nakashima Takuya、Rapenne Gwenael、Kawai Tsuyoshi
  • Journal Title: The Journal of Organic Chemistry Volume: 83 Issue: 22 Pages: 13700-13706
  • DOI: 10.1021/acs.joc.8b01877
  • Peer Reviewed / Int'l Joint Research
• [Presentation] フォトクロミックターアリーレーンの連鎖的酸化開環反応における熱発生 (2019)
  • Author(s): 関口友貴 中嶋琢也 河合壯
  • Organizer: 日本化学会第99春季年会
• [Presentation] ターアリーレン系フォトクロミック分子の高感度化と酸発生剤への展開 (2018)
  • Author(s): 河合壯
  • Organizer: フォトポリマー懇話会講演会
  • Invited
• [Presentation] ターアリーレン骨格を基盤とした光誘起カルボカチオン発生剤の創成 (2018)
  • Author(s): 水津了 河合壯
  • Organizer: 第39回光化学若手の会
• [Presentation] Terarylene Photogenerators as Sources of Acids, Superacids and Hydrides (2018)
  • Author(s): Colin Martin TAKUYA NAKASHIMA TSUYOSHI KAWAI
  • Organizer: 27th photo IUPAC
  • Int'l Joint Research
• [Presentation] X-Ray Induced Amplified Cycloreversion of Photochromic Terarylene (2018)
  • Author(s): 朝戸良輔 TAKUYA NAKASHIMA TSUYOSHI KAWAI
  • Organizer: 27th photo IUPAC
  • Int'l Joint Research
• [Presentation] Molecular Thermal Strage (MOST) and Thermal Release with Photochromic Terarylene (2018)
  • Author(s): 朝戸良輔 中嶋琢也 河合壯
  • Organizer: 2018年 光化学討論会
• [Presentation] フォトクロミックターアリーレンを用いた分子光熱貯蓄変換材料の開発 (2018)
  • Author(s): 朝戸良輔 中嶋琢也 河合壯
  • Organizer: 第79回応用物理学会 秋季学術講演会
  • Invited
• [Presentation] フォト・エレクトロクロミック分子の超連鎖反応が開く新機能 (2018)
  • Author(s): 河合壯
  • Organizer: フォトエレクトロクロミック分子の超連鎖反応が開く新機能
  • Invited
• [Remarks] 光反応分子科学研究室
  • URL: https://mswebs.naist.jp/LABs/kawai/index.html
• [Remarks] 奈良先端科学技術大学院大学光反応分子科学研究室
  • URL: https://mswebs.naist.jp/LABs/kawai/index.html
• [Remarks] 奈良先端科学技術大学院大学 光情報分子科学研究室
  • URL: https://mswebs.naist.jp/LABs/kawai/index.html