Bridge-Mediated Dynamic Exciton

• Project Area: Dynamic Exciton: Emerging Science and Innovation
• Project/Area Number: 20H05832
• Research Category: Grant-in-Aid for Transformative Research Areas (A)
• Allocation Type: Single-year Grants
• Review Section: Transformative Research Areas, Section (II)
• Research Institution: Kyoto University
• Principal Investigator: 今堀 博 京都大学, 工学研究科, 教授 (90243261)
• Co-Investigator(Kenkyū-buntansha): 梅山 有和 兵庫県立大学, 工学研究科, 教授 (30378806) ; 長谷川 美貴 青山学院大学, 理工学部, 教授 (70306497)
• Project Period (FY): 2020-11-19 – 2025-03-31
• Project Status: Granted (Fiscal Year 2024)
• Budget Amount: ¥163,930,000 (Direct Cost: ¥126,100,000、Indirect Cost: ¥37,830,000); Fiscal Year 2024: ¥28,600,000 (Direct Cost: ¥22,000,000、Indirect Cost: ¥6,600,000); Fiscal Year 2023: ¥28,600,000 (Direct Cost: ¥22,000,000、Indirect Cost: ¥6,600,000); Fiscal Year 2022: ¥28,600,000 (Direct Cost: ¥22,000,000、Indirect Cost: ¥6,600,000); Fiscal Year 2021: ¥27,040,000 (Direct Cost: ¥20,800,000、Indirect Cost: ¥6,240,000); Fiscal Year 2020: ¥51,090,000 (Direct Cost: ¥39,300,000、Indirect Cost: ¥11,790,000)
• Keywords: ドナー・アクセプター相互作用 / 光電荷分離 / 有機太陽電池モデル / 振電相互作用 / スピン軌道相互作用 / 有機太陽電池 / 電相互作用

Outline of Research at the Start

光化学は、エレクトロニクス、エネルギー、医薬・医療、機能性材料など現代社会において多様な貢献を期待されている。その根幹を司る有機分子のドナー(D)・アクセプター(A) 相互作用は、これまで励起子における電荷移動(CT)状態を、クーロン相互作用で束縛された静的エキシトンとして捉えてきた。しかし、D・A 系では核や格子の運動、スピン軌道相互作用が動的効果として時間発展的に働く。そこで、本研究課題では、動的エキシトン効果が励起・CT・電荷分離状態に与える影響を解明するためのモデルとして、有機分子による精緻なD・A 系を設計・合成し、その基礎学理を構築する。さらに、有機太陽電池材料への展開を行う。

Outline of Annual Research Achievements

本研究では、ドナー(D)とアクセプター(A)を、共有結合や配位結合により架橋することで、孤立系または凝集系における光電荷分離モデル系を創出する。それらを用いて、光電荷分離過程においてD・A分子の動的相互作用を有効に引き出すための学理を構築し、有機太陽電池の高効率化に向けた材料設計指針を得る。共有結合を用いる系では、D・A 分子間の距離や配向が明確であり、架橋子を介したD・A間の軌道の重なりが精密に制御され、かつ選択的な振動励起が可能なD・A 連結モデル系を系統的に創出する。これにより架橋子を含めたD・A分子の核の配置や運動性が、スピン軌道相互作用によるスピン変換や電荷移動性状態・電荷分離状態に与える影響を詳細に調べる。また、配位結合を利用して基板上に金属有機構造体を構築する手法(SURMOF法)により、D・A分子を精密配列制御することで、凝集系D/A界面構造のモデル系を構築する。
具体的には、D・A 連結分子の架橋子構造に着目した。系統的に構造を変化させた架橋子でD・A 分子を共有結合連結することで、D・A 分子間の距離や配向 、架橋子を介したD・A 間の軌道の重なりの精密制御が可能である。さらに、中赤外光により選択的に振動励起できる３重結合、CN、C=O などの官能基を架橋子、さらにD・A 部位に導入することで、電子励起と振動励起を同時に起こすことを考えた。そして、D・A分子の核の配置や運動が、どのように電荷分離やスピン変換挙動に影響を与えるのか、という問いに取り組んだ。一方、SURMOF法によりD・A 分子を配列制御することで、有機太陽電池のD/A 界面構造のモデル系を構築することを計画した。モデル系の構造と光物性を詳細に調べることで、D・A 分子の核の配置や運動が、どのように光電荷分離挙動に影響を与えるのか、という問いに取り組んだ。

Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

架橋子構造に着目したD・A 連結分子を設計、合成した。特に、中赤外光により選択的に振動励起できる３重結合、C=O などの官能基を架橋子、さらにD・A 部位に導入することで、電子励起と振動励起を同時に起こせると考えて、分子を合成した。一方、SURMOF法によりD・A 分子を配列制御することで、有機太陽電池のD/A 界面構造のモデル系を構築することを計画した。D・A 分子を設計、合成し、SURMOF作製を共同研究先の中国大連理工学大学に依頼し、D・A 分子それぞれでSUFMOFが作製できることを確認した。さらに、有機太陽電池のD/A 界面構造のモデル系として、独自に開発したA-D-A型の非フラーレンアクセプターとその光電荷分離モデル分子の超分子形成と光ダイナミクスを明らかにした。

Strategy for Future Research Activity

中赤外光により選択的に振動励起できる３重結合、C=O などの官能基を架橋子、さらにD・A 部位に導入したD1-D2-A 連結分子の参照化合物を合成する。電子励起と振動励起により、光電荷分離過程を制御することを試みる。一方、SURMOF法によりD・A 分子を同時に配列制御することで、有機太陽電池のD/A 界面構造のモデルSURMOF作製を試みる。一方、有機太陽電池のD/A 界面構造のモデル系として、ポルフィリン・フラーレン連結系を検討する。

Research Products

• [Int'l Joint Research] 大連理工大学(中国)
• [Int'l Joint Research] 大連理工大学(中国)
• [Int'l Joint Research] 大連理工大学(中国)
• [Int'l Joint Research] タンペレ工科大学(フィンランド)
• [Int'l Joint Research] ノルウェー北極大学(ノルウェー)
• [Journal Article] Unraveling complex performance-limiting factors of brominated ITIC derivative: PM6 organic solar cells by using time-resolved measurements (2023)
  • Author(s): S. Li, R. Nishikubo, T. Wada, T. Umeyama, H. Imahori, A. Saeki
  • Journal Title: Polymer Journal Volume: 55 Issue: 4 Pages: 463-476
  • DOI: 10.1038/s41428-022-00704-1
  • Peer Reviewed
• [Journal Article] Truxenone Triimide: Two‐Dimensional Molecular Arrangements of Triangular Molecules for Air Stable n‐Type Semiconductors (2022)
  • Author(s): Kumar Sharvan、Koo Yun Hee、Higashino Tomohiro、Matsuda Wakana、Ghosh Samrat、Tsutsui Yusuke、Suda Masayuki、Imahori Hiroshi、Suzuki Katsuaki、Kaji Hironori、Seki Shu
  • Journal Title: Advanced Electronic Materials Volume: - Issue: 7 Pages: 2101390-2101390
  • DOI: 10.1002/aelm.202101390
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Rational Synthesis of Benzoheterole-fused Porphyrins and π-System Switching by Central Metal Ion (2022)
  • Author(s): Higashino Tomohiro、Iizumi Rikiya、Imahori Hiroshi
  • Journal Title: Chemistry Letters Volume: 51 Issue: 9 Pages: 932-935
  • DOI: 10.1246/cl.220277
  • Peer Reviewed
• [Journal Article] Emergence of Copper(I/II) Complexes as Third-Generation Redox Shuttles for Dye-Sensitized Solar Cells (2022)
  • Author(s): T. Higashino and H. Imahori
  • Journal Title: ACS Energy Lett. Volume: 7 Pages: 1926-1938
  • Peer Reviewed
• [Journal Article] Citric Acid-Based Carbon Dots and Their Application in Energy Conversion (2022)
  • Author(s): L. Vallan and H. Imahori
  • Journal Title: ACS Appl. Electronic Mater. Volume: 4 Issue: 9 Pages: 4231-4257
  • DOI: 10.1021/acsaelm.2c01021
  • Peer Reviewed
• [Journal Article] Facile synthesis of an ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion: from serendipity to design (2022)
  • Author(s): Kumar Sharvan、Yoshida Kohshi、Hattori Yusuke、Higashino Tomohiro、Imahori Hiroshi、Seki Shu
  • Journal Title: Chemical Science Volume: 13 Issue: 6 Pages: 1594-1599
  • DOI: 10.1039/d1sc06070h
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Donor-π-Acceptor Type Porphyrin-Fullerene Dyad with Acetylene Bridge for p-Type Dye-sensitized Solar Cell (2022)
  • Author(s): Qi Guo, Tomohiro Higashino, Kosaku Kato, Akira Yamakata, Hiroshi Imahori
  • Journal Title: Chemistry Letters Volume: 51 Issue: 3 Pages: 260-263
  • DOI: 10.1246/cl.210717
  • Peer Reviewed
• [Journal Article] Prolongation of the Singlet Exciton Lifetime of Nonfullerene Acceptor Films by the Replacement of the Central Benzene Core with Naphthalene (2021)
  • Author(s): T. Umeyama, K. Igarashi, Y. Tamai, T. Wada, T. Takeyama, D. Sasada, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, H. Ohkita, and H. Imahori
  • Journal Title: Sus. Energy Fuels Volume: 5 Issue: 7 Pages: 2028-2035
  • DOI: 10.1039/d0se01861a
  • Peer Reviewed
• [Journal Article] Photodynamic and Photoelectrochemical Properties of Few-Layered Bismuthene Film on SnO2 Electrode and Its Hybridization with C60 (2021)
  • Author(s): Umeyama Tomokazu、Xu Han、Ohara Tomoya、Tsutsui Yusuke、Seki Shu、Imahori Hiroshi
  • Journal Title: The Journal of Physical Chemistry C Volume: 125 Issue: 25 Pages: 13954-13962
  • DOI: 10.1021/acs.jpcc.1c03574
  • Peer Reviewed
• [Journal Article] Long-Range Interfacial Charge Carrier Trapping in Halide Perovskite-C60 and Halide Perovskite-TiO2 Donor-Acceptor Films (2021)
  • Author(s): Bhagyashree, M. S., Okamoto, T., Ghimire, S., Umeyama, T., Takano, Y., Imahori, H., Biju, V.
  • Journal Title: The Journal of Physical Chemistry Letters Volume: 12 Issue: 35 Pages: 8644-8651
  • DOI: 10.1021/acs.jpclett.1c01909
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis of Thiophene-Fused Porphyrin Dimers as Effective pi-Extended Helical Chromophores (2021)
  • Author(s): I. Nishimra, T. Higasino, and H. Imahori
  • Journal Title: Chem. Commun. Volume: 57 Issue: 75 Pages: 9606-9609
  • DOI: 10.1039/d1cc04215g
  • Peer Reviewed
• [Journal Article] Effect of Terminal-Group Halogenation of Naphthalene-Based Nonfullerene Acceptors on Their Film Structure and Photophysical and Photovoltaic Properties (2021)
  • Author(s): Tomokazu Umeyama, Tatsuho Wada, Kensho Igarashi, Kosaku Kato, Akira Yamakata, Taiki Takeyama, Yuji Sakamoto, Yasunari Tamai, Hideo Ohkita, Keiichi Ishida, Tomoyuki Koganezawa, Shunsuke Ohtani, Kazuo Tanaka, Hiroshi Imahori
  • Journal Title: ACS APPlied Energy Materials Volume: 4 Issue: 12 Pages: 14022-14033
  • DOI: 10.1021/acsaem.1c02816
  • Peer Reviewed / Open Access
• [Journal Article] Thiophene‐Fused Naphthodiphospholes: Modulation of the Structural and Electronic Properties of Polycyclic Aromatics by Precise Fusion of Heteroles (2021)
  • Author(s): Ishida Keiichi、Higashino Tomohiro、Wada Yoshimasa、Kaji Hironori、Saeki Akinori、Imahori Hiroshi
  • Journal Title: ChemPlusChem Volume: 86 Issue: 1 Pages: 130-136
  • DOI: 10.1002/cplu.202000800
  • Peer Reviewed
• [Journal Article] Development of Clean Performance-Tunable Waterborne Polyurethane Using Acetyl Tributyl Citrate for Transferable Holographic Films (2021)
  • Author(s): X.-G. Li, Y.-B. Xie, M.-R. Huang, T. Umeyama, and H. Imahori
  • Journal Title: J. Clean. Prod. Volume: 279 Pages: 123496-123496
  • DOI: 10.1016/j.jclepro.2020.123496
  • Peer Reviewed
• [Journal Article] Noncovalent Functionalization of Few-Layered Antimonene with Fullerene Clusters and Photoinduced Charge Separation in the Composite (2020)
  • Author(s): T. Umeyama, T. Ohara, Y. Tsutsui, S. Nakano, S. Seki, and H. Imahori
  • Journal Title: Chem. Eur. J. Volume: 26 Issue: 29 Pages: 6726-6735
  • DOI: 10.1002/chem.202001740
  • Peer Reviewed
• [Journal Article] Exploration on the Combination of Push-Pull Porphyrin Dyes and Copper(I/II) Redox Shuttles toward High-Performance Dye-Sensitized Solar Cells (2020)
  • Author(s): T. Higashino, H. Iiyama, I. Nishimura, and H. Imahori
  • Journal Title: Chem. Lett. Volume: 49 Issue: 8 Pages: 936-939
  • DOI: 10.1246/cl.200317
  • NAID: 130007884738
  • Peer Reviewed
• [Journal Article] Efficient Exciton Diffusion in Micrometer-Sized Domains of Nanographene-Based Non-Fullerene Acceptors with Long Exciton Lifetimes in Blend Films with Conjugated Polymer (2020)
  • Author(s): T. Umeyama, K. Igarashi, D. Sasada, K. Ishida, T. Koganezawa, S. Ohtani, K. Tanaka, and H. Imahori
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 12 Issue: 35 Pages: 39236-39244
  • DOI: 10.1021/acsami.0c10834
  • Peer Reviewed
• [Journal Article] Elucidation of the Mechanisms for the Underlying Depolarization and Reversibility by Photoactive Molecule. (2020)
  • Author(s): Numata Tomohiro、Fukuda Ryosuke、Hirano Mitsuru、Yamaguchi Kazuma、Sato-Numata Kaori、Imahori Hiroshi、Murakami Tatsuya
  • Journal Title: Cellular Physiology and Biochemistry Volume: 54 Issue: 5 Pages: 899-916
  • DOI: 10.33594/000000277
  • Peer Reviewed / Open Access
• [Journal Article] Unique Role of Heterole-fused Structures in Aromaticity and Physicochemical Properties of 7,8-Dehydropurpurins (2020)
  • Author(s): T. Higashino, I. Nishimura, and H. Imahori
  • Journal Title: Chem. Eur. J. Volume: 52 Issue: 52 Pages: 12043-12049
  • DOI: 10.1002/chem.202001361
  • Peer Reviewed
• [Journal Article] Near-infrared light control of membrane potential by an electron donor-acceptor linked molecule (2020)
  • Author(s): Yuta Takano, Kazuaki Miyake, Jeladhara Sobhanan, Vasudevanpillai Biju, Nikolai V Tkachenko, Hiroshi Imahori
  • Journal Title: Chemical Communications Volume: 56 Issue: 83 Pages: 12562-12565
  • DOI: 10.1039/d0cc05326k
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins (2020)
  • Author(s): M. Morisue, G. Saito, D. Sasada, T. Umeyama, H. Imahori, K. Mitamura, H. Masunaga, T. Hoshino, S. Sakurai, S. Sasaki
  • Journal Title: Langmuir Volume: 36 Issue: 45 Pages: 13583-13590
  • DOI: 10.1021/acs.langmuir.0c02427
  • Peer Reviewed
• [Journal Article] Heavy Metal Effects on the Photovoltaic Properties of Metallocorroles in Dye-Sensitized Solar Cells (2020)
  • Author(s): Tomohiro Higashino, Yuma Kurumisawa, Abraham B. Alemayehu, Rune F. Einrem, Debashis Sahu, Daniel Packwood, Kosaku Kato, Akira Yamakata, Abhik Ghosh and Hiroshi Imahori
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 12 Pages: 12460-12467
  • DOI: 10.1021/acsaem.0c02427
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Rational Design of Dyes and Donor-Acceptor Type Molecules for Organic Solar Cells (2022)
  • Author(s): H. Imahori
  • Organizer: 241th Meeting of The Electrochemical Society
  • Int'l Joint Research / Invited
• [Presentation] Molecular Engineering of Organic Photovoltaics (2022)
  • Author(s): H. Imahori
  • Organizer: The 29th International Workshop on Active-Matrix Flatpanel Displays and Devices (AM-FPD 22)
  • Int'l Joint Research / Invited
• [Presentation] Porphyrins and Corroles for Dye-Sensitized Solar Cells (2022)
  • Author(s): H. Imahori
  • Organizer: 12th International Conference on Porphyrins and Phthalocyanine (ICPP12)
  • Int'l Joint Research / Invited
• [Presentation] Molecular Design Strategies for High-Performance Organic Photovoltaics (2022)
  • Author(s): H. Imahori
  • Organizer: Annual Meeting on Photochemistry 2022
  • Invited
• [Presentation] Molecular Photoinduced Charge Separation and Energy/Biological Applications (2022)
  • Author(s): H. Imahori
  • Organizer: The 103rd CSJ Annual Meeting
  • Invited
• [Presentation] Rational Molecular Design of Nonfullerene Acceptors for Bulk Heterojunction Solar Cells (2021)
  • Author(s): H. Imahori
  • Organizer: 239th Meeting of The Electrochemical Society
  • Int'l Joint Research / Invited
• [Presentation] Dynamic Exciton: Manipulation of Charge-Transfer States (2021)
  • Author(s): H. Imahori
  • Organizer: International Congress on Energy Chemistry and Engineering (ICECE-2021)
  • Int'l Joint Research / Invited
• [Presentation] Porphyrins for Model Systems and Organic Solar Cells (2021)
  • Author(s): H. Imahori
  • Organizer: International Conference on Porphyrins and Phthalocyanines (ICPP-11)
  • Int'l Joint Research / Invited
• [Presentation] Molecular Engineering of Photoinduced Charge Separation (2021)
  • Author(s): H. Imahori
  • Organizer: ECS Webinar
  • Int'l Joint Research / Invited
• [Presentation] Molecular Engineering of Donor-Acceptor Systems toward Dynamic Exciton (2021)
  • Author(s): H. Imahori
  • Organizer: The International Conference on Flexible and Printed Electronics (ICFPE)
  • Int'l Joint Research / Invited
• [Presentation] Photoinduced Energy and Electron Transfer in Donor-Acceptor Model Systems and Organic Solar Cells (2021)
  • Author(s): H. Imahori
  • Organizer: Pacifichem 2015, Symposium #414
  • Int'l Joint Research / Invited
• [Presentation] “Dynamic Exciton”: Manipulation of Charge-Transfer States toward Energy and Synthetic/Biological Applications (2021)
  • Author(s): H. Imahori
  • Organizer: Pacifichem 2015, Symposium #218
  • Int'l Joint Research / Invited
• [Presentation] 分子工学に基づいた有機太陽電池材料の創製 (2020)
  • Author(s): 今堀 博
  • Organizer: 近畿化学協会 機能性色素部会第101回例会「有機太陽電池の最新動向と新展開」
  • Invited
• [Presentation] Photoinduced Energy and Electron Transfer in Nanocarbon-Based Donor-Acceptor Systems (2020)
  • Author(s): H. Imahori
  • Organizer: Pacific Rim Meeting on Electrochemical and Solid-State Science (PRiME 2020)
  • Int'l Joint Research
• [Remarks] Publications
  • URL: http://www.moleng.kyoto-u.ac.jp/~moleng_05/publications/