Elucidation of natural and artificial photosynthetic processes by realtime and state-selective analytical methods

• Project Area: Creation of novel light energy conversion system through elucidation of the molecular mechanism of photosynthesis and its artificial design in terms of time and space
• Project/Area Number: 20H05106
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Complex systems
• Research Institution: Kyushu University
• Principal Investigator: 恩田 健 九州大学, 理学研究院, 教授 (60272712)
• Project Period (FY): 2020-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000); Fiscal Year 2021: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2020: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 人工光合成 / 時間分解赤外 / CO2還元 / 金属錯体 / 光機能性材料 / 時間分解赤外分光 / 光化学 / 光機能性分子 / 時間分解振動分光 / 錯体化学 / 超分子錯体 / 天然光合成

Outline of Research at the Start

天然および人工光合成過程は、多くの化学種が関与した多光子、多電子過程である。そのため従来の反応分析法では、そのメカニズムを理解し、高効率で安価な光合成系を人工的に構築することは困難である。そこで本研究では、実時間で化学種およびその状態を選別して測定が可能な各種時間分解振動分光を開発し、さらにそれらを用いて主要な反応過程の機構解明を目的とする。これらの結果を系統的、総合的に理解することにより、複雑な光合成過程の理解、それに基づく人工光合成系の開発に貢献する。

Outline of Annual Research Achievements

光-物質変換過程のように分子の光励起状態を経由する化学反応過程は、光活性種生成直後のフェムト秒から後続の熱的反応が起こるミリ秒まで幅広い時間領域で起こっている。さらに、その間に複数の化学種、電子が関与することから、反応機構解明のためには高い時間分解能、広い測定時間領域に加え、短寿命な化学種およびその状態を選別して観測できる分析手段が求められている。そこで本研究では、その高いエネルギー分解能から状態選別性の高い時間分解赤外分光法に着目し、より複雑な反応系における微量物質の検出が可能な装置およびそのデータ解析法の開発を行った。さらに複雑な系の分析には、同一条件で多くのプローブ手段を相補的に用いることが必要である。そこで、同じ試料に適用可能な時間分解発光分光装置、近赤外から紫外までの過渡吸収分光装置の開発も行った。これらに加え、特に過渡的分子構造決定に有効な時間分解電子線回折、時間分解X線吸収分光測定も、それぞれを専門とするグループとの共同研究によって可能とした。これら装置を用いて、CO2光還元触媒系において、Re(I)カルボニル錯体の励起状態の構造決定とその光物性との関係の解明、主要な中間体である一電子還元CO2付加体の直接観測を行った。また安価な光増感剤として様々な応用の期待されるCu(I)錯体の長励起状態寿命(>100 us)の原因も明らかにした。さらに、CO2光還元半導体-金属錯体複合体における電子移動過程の解明、強い光吸収を示し安定なポルフィリンおよびフタロシアニンを用いた反応系、銅、鉄などの安価な金属を用いた反応系の光過程解明なども行った。さらに開発した計測システムおよび解析手段を応用して、発光性配位高分子、有機発光材料、光誘起酸素輸送材料など、多くのこれまで実時間観測の対象となっていなかった光機能性物質の測定を行い、その動的過程と光機能の関係を詳細に明らかにした。

Research Progress Status

令和3年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和3年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Characterisation of Excited States in a Multiple-Resonance-Type Thermally Activated Delayed Fluorescence Molecule Using Time-Resolved Infrared Spectroscopy (2022)
  • Author(s): M. Saigo, Y. Shimoda, T. Ehara, T. Ryu, K. Miyata, K. Onda
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 95 Issue: 3 Pages: 381-388
  • DOI: 10.1246/bcsj.20210403
  • Peer Reviewed
• [Journal Article] Aggregation-induced emission active thermally-activated delayed fluorescence materials possessing N-heterocycle and sulfonyl groups (2022)
  • Author(s): Matsui Yasunori、Yokoyama Yudai、Ogaki Takuya、Ishiharaguchi Kenta、Niwa Akitsugu、Ohta Eisuke、Saigo Masaki、Miyata Kiyoshi、Onda Ken、Naito Hiroyoshi、Ikeda Hiroshi
  • Journal Title: Journal of Materials Chemistry C Volume: 10 Issue: 12 Pages: 4607-4613
  • DOI: 10.1039/d1tc05196b
  • Peer Reviewed / Open Access
• [Journal Article] Heavy metal-free visible-to-UV photon upconversion with over 20% efficiency sensitized by a ketocoumarin derivative (2022)
  • Author(s): Uji Masanori、Harada Naoyuki、Kimizuka Nobuo、Saigo Masaki、Miyata Kiyoshi、Onda Ken、Yanai Nobuhiro
  • Journal Title: Journal of Materials Chemistry C Volume: 10 Issue: 12 Pages: 4558-4562
  • DOI: 10.1039/d1tc05526g
  • Peer Reviewed
• [Journal Article] Low-threshold exciton-polariton condensation via fast polariton relaxation in an organic microcavities (2021)
  • Author(s): T. Ishii, K. Miyata, M. Mamada, F. Bencheikh, F. Mathevet, K. Onda, S. Kena-Cohen, C. Adachi
  • Journal Title: Adv. Opt. Mater. Volume: 10 Issue: 3 Pages: 2102034-2102034
  • DOI: 10.1002/adom.202102034
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Enhanced light-matter interaction and polariton relaxation by the control of molecular orientation (2021)
  • Author(s): T. Ishii, F. Bencheikh, S. Forget, S. Chenais, B. Heinrich, D. Kreher, L. S. Vargas, K. Miyata, K. Onda, T. Fujihara, S. Kena-Cohen, F. Mathevet, C. Adachi
  • Journal Title: Adv. Opt. Mater. Volume: 10 Issue: 22 Pages: 2101048-2101048
  • DOI: 10.1002/adom.202101048
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Photoinduced Oxygen Transport in Cobalt Double-Perovskite Crystal EuBaCo2O5.39 (2021)
  • Author(s): M. Hada, S. Ohmura, T. Ishikawa, M. Saigo, N. Keio, W. Yajima, T. Suzuki, D. Urushihara, K. Takubo, Y. Masaki, M. Kuwahara, K. Tsuruta, Y. Hayashi, J. Matsuo, T. Yokoya, K. Onda, F. Shimojo, M. Hase, S. Ishihara, T. Asaka, N. Abe, T. Arima, S. Koshihara, Y. Okimoto
  • Journal Title: Appl. Mater. Today Volume: 24 Pages: 101167-101167
  • DOI: 10.1016/j.apmt.2021.101167
  • Peer Reviewed / Open Access
• [Journal Article] Achieving Thermally Activated Delayed Fluorescence from Benzophenone by Host-Guest Complexation (2021)
  • Author(s): R. K. Koninti, K. Miyata, M. Saigo, K. Onda
  • Journal Title: J. Phys. Chem. C Volume: 125 Issue: 31 Pages: 17392-17399
  • DOI: 10.1021/acs.jpcc.1c04283
  • Peer Reviewed
• [Journal Article] Mechanistic study of Photocatalytic CO2 reduction using Ru(II)-Re(I) supramolecular photocatalyst (2021)
  • Author(s): K. Kamogawa, Y. Shimoda, K. Miyata, K. Onda, Y. Yamazaki, Y. Tamaki, O. Ishitani
  • Journal Title: Chem. Sci. Volume: 12 Issue: 28 Pages: 9682-9693
  • DOI: 10.1039/d1sc02213j
  • Peer Reviewed / Open Access
• [Journal Article] Determining Excited-State Structures and Photophysical Properties in Phenylphosphine Rhenium(I) Diimine Biscarbonyl Complexes Using Time-Resolved Infrared and X-ray Absorption Spectroscopies (2021)
  • Author(s): Yuushi Shimoda, Kiyoshi Miyata, Masataka Funaki, Takumi Ehara, Tatsuki Morimoto, Shunsuke Nozawa, Shin-ichi Adachi, Osamu Ishitani, Ken Onda
  • Journal Title: Inorganic Chemistry Volume: 60 Issue: 11 Pages: 7773-7784
  • DOI: 10.1021/acs.inorgchem.1c00146
  • Peer Reviewed / Open Access
• [Journal Article] Guest-Tunable Excited States in a Cyanide-Bridged Luminescent Coordination Polymer (2021)
  • Author(s): Sasaki Kenta、Yoshino Haruka、Shimoda Yuushi、Saigo Masaki、Miyata Kiyoshi、Onda Ken、Sugimoto Kunihisa、Yamate Hitomi、Miura Hiroki、Le Ouay Benjamin、Ohtani Ryo、Ohba Masaaki
  • Journal Title: Inorganic Chemistry Volume: 60 Issue: 9 Pages: 6140-6146
  • DOI: 10.1021/acs.inorgchem.1c00702
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Coordination geometrical effect on LMCT-depended energy transfer processes of luminescent Eu(III) complexes (2021)
  • Author(s): Pedro Paulo Ferreira da Rosa, Shiori Miyazaki, Haruna Sakamoto, Yuichi Kitagawa, Kiyoshi Miyata, Tomoko Akama, Masato Kobayashi, Koji Fushimi, Ken Onda, Tetsuya Taketsugu, Yasuchika Hasegawa
  • Journal Title: J Phys. Chem. A Volume: 125 Issue: 1 Pages: 209-217
  • DOI: 10.1021/acs.jpca.0c09337
  • Peer Reviewed
• [Journal Article] Picosecond dynamics in layered cobalt perovskites studied by time-resolved Raman spectroscopy (2021)
  • Author(s): Fukaya Ryo、Yamaya Nao、Ishikawa Tadahiko、Koshihara Shin-ya、Okimoto Yoichi、Onda Ken、Isayama Akira、Sasagawa Takao、Horigane Kazumasa
  • Journal Title: Comptes Rendus. Physique Volume: 22 Issue: S2 Pages: 1-8
  • DOI: 10.5802/crphys.35
  • Peer Reviewed / Open Access
• [Journal Article] Study of excited states and electron transfer of semiconductor-metal complex hybrid photocatalysts for CO2 reduction using picosecond time-resolved spectroscopies", (2020)
  • Author(s): Shunsuke Sato, Sei'ichi Tanaka, Ken-ichi Yamanaka, Shu Saeki, Keita Sekizawa, Takeshi Morikawa, Ken Onda
  • Journal Title: Chem. Eur. J. Volume: 27 Issue: 3 Pages: 1127-1137
  • DOI: 10.1002/chem.202004068
  • Peer Reviewed
• [Journal Article] Intramolecular-Rotation Driven Triplet-to-Singlet Upconversion and Fluctuation Induced Fluorescence Activation in Linearly-Connected Donor-Accepter Molecules (2020)
  • Author(s): Yuushi Shimoda, Kiyoshi Miyata, Masaki Saigo, Youichi Tsuchiya, Chihaya Adachi, Ken Onda
  • Journal Title: J. Chem. Phys. Volume: 153 Issue: 20 Pages: 204702-204702
  • DOI: 10.1063/5.0029608
  • Peer Reviewed
• [Journal Article] Vapor Switching of the Luminescence Mechanism in a Re(v) Complex (2020)
  • Author(s): Kenta Sasaki, Hitomi Yamate, Haruka Yoshino, Hiroki Miura, Yuushi Shimoda, Kiyoshi Miyata, Ken Onda, Ryo Ohtani, Masaaki Ohba
  • Journal Title: Chem. Commun. Volume: 56 Issue: 85 Pages: 12961-12964
  • DOI: 10.1039/d0cc05462c
  • Peer Reviewed
• [Journal Article] Dual Energy Transfer Pathways from an Antenna Ligand to Lanthanide Ion in Trivalent Europium Complexes with Phosphine-Oxide Bridges (2020)
  • Author(s): Shiori Miyazaki, Kiyoshi Miyata, Haruna Sakamoto, Fumiya Suzue, Yuichi Kitagawa, Yasuchika Hasegawa, Ken Onda
  • Journal Title: J. Phys. Chem. A Volume: 124 Issue: 33 Pages: 6601-6606
  • DOI: 10.1021/acs.jpca.0c02224
  • Peer Reviewed
• [Presentation] Tracking the multi-step and multi-electron CO2 reduction photocatalytic processes using time-resolved infrared spectroscopy (2021)
  • Author(s): Ken Onda
  • Organizer: The 2021 International Chemical Congress of Pacific Basin Societies
  • Int'l Joint Research / Invited
• [Presentation] Time-resolved Spectroscopic Studies on Elementary Processes in Photofunctional Metal Complexes (2021)
  • Author(s): Ken Onda
  • Organizer: The 4th International Symposium on Photofunctional Chemistry of Complex Systems (ISPCCS 2021)
  • Int'l Joint Research / Invited
• [Presentation] Fundamental mechanisms of artificial photosynthesis studied by time-resolved infrared spectroscopy (2021)
  • Author(s): Ken Onda
  • Organizer: 11th Asian Photochemistry Conference
  • Int'l Joint Research / Invited
• [Presentation] 発光性希土類錯体におけるエネルギー移動機構の解明 (2021)
  • Author(s): 恩田健、宮崎栞、宮田潔志
  • Organizer: 第383回蛍光体同学会講演会
  • Invited
• [Presentation] 時間分解赤外分光を用いた光機能性物質の動的構造解析 (2021)
  • Author(s): 恩田健
  • Organizer: 一般社団法人レーザー学会学術講演会第41回年次大会
  • Invited
• [Presentation] Structural Dynamics in Photofunctional Materials Studied by Time-resolved Infrared Spectroscopy (2020)
  • Author(s): Ken Onda
  • Organizer: RIKEN CEMS Topical Meeting
  • Invited
• [Presentation] Detailed Analysis of Emitting Processes of Emitters for OLED using Time-resolved Vibrational Spectroscopy (2020)
  • Author(s): Ken Onda, Masaki Saigo, Yuushi Shimoda, Kiyoshi Miyata
  • Organizer: The 27th International Display Workshops
  • Int'l Joint Research / Invited
• [Book] 時間分解赤外分光 (2021)
  • Author(s): 日本化学会、恩田 健
  • Total Pages: 196
  • Publisher: 共立出版
  • ISBN: 9784320044807
• [Book] 時間分解赤外分光 光化学反応の瞬間を診る (2021)
  • Author(s): 恩田 健
  • Total Pages: 196
  • Publisher: 共立出版
  • ISBN: 9784320044807
• [Remarks] 九州大学 分光分析化学研究室
  • URL: http://www.chem.kyushu-univ.jp/Spectrochem/
• [Remarks] 九州大学理学研究院化学部門分光分析化学研究室
  • URL: http://www.scc.kyushu-u.ac.jp/Spectrochem/
• [Remarks] 業績リスト 恩田健
  • URL: http://www.scc.kyushu-u.ac.jp/Spectrochem/onda.html