Breakthrough in Chiral Photochemistry based on the Excitation of Charge-Transfer Complex

• Project/Area Number: 18H01964
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Osaka University
• Principal Investigator: 森 直 大阪大学, 工学研究科, 准教授 (70311769)
• Co-Investigator(Kenkyū-buntansha): 西嶋 政樹 東北大学, 多元物質科学研究所, 助教 (70448017)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000); Fiscal Year 2021: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2020: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2019: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2018: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000)
• Keywords: 光不斉反応 / 電荷移動錯体 / エキシプレックス / エントロピー制御 / キラリティー / 可視光励起 / キラルルイス酸 / 励起三重項 / ＣＴ錯体

Outline of Annual Research Achievements

電子供与体と受容体は、基底状態において弱い相互作用を示し、可視光領域に電荷移動吸収帯を有する電荷移動錯体を生成する。この波長選択的な光励起により励起電荷移動錯体が生成するが、これまでの研究でこの励起種が通常のエキシプレックスとは異なる励起種であり、特異な光反応性、立体選択性を示すことが明らかとなっている。本年度は、励起三重項状態の関与するキラル光反応、具体的にはナフトキノンへのアルケンの分子内付加反応において、電荷移動励起を検討するとともにキラルルイス酸の配位効果を検討した。天然物などに多く存在する複雑な多環式化合物を高い立体選択性で生成可能となれば合成反応としても有意義であり、その立体選択性の支配因子を解明することが重要である。具体的な成果としては、予測した通常の環化生成物に加え、交差型の極めて特異な多環式化合物が比較的高い収率で生成していることをＸ線結晶構造などの解析により明らかとした。また、生成物の絶対配置を円二色スペクトルなどの検討により決定することができた。ルイス酸の配位は基底状態では共同的であるが、励起状態では錯形成能が低下する傾向が見られた。このため、適切な濃度のルイス酸を添加することで、立体選択性を高めることに成功し、最大70%ee程度にまで向上することが可能となった。関連研究はNature Communication誌など7報の論文で報告した。本研究の主たる成果の全容は論文として投稿中であり、掲載が待たれる。

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

• [Int'l Joint Research] ミュンヘン工科大学(ドイツ)
• [Int'l Joint Research] 四川大学(中国)
• [Int'l Joint Research] ミュンヘン工科大学(ドイツ)
• [Int'l Joint Research] 四川大学(中国)
• [Int'l Joint Research] ミュンヘン工科大学(ドイツ)
• [Int'l Joint Research] 四川大学(中国)
• [Int'l Joint Research] ミュンヘン工科大学(ドイツ)
• [Int'l Joint Research] 四川大学(中国)
• [Journal Article] Cyclodextrins with Multiple Pyrenyl Groups: An Approach to Organic Molecules Exhibiting Bright Excimer Circularly Polarized Luminescence (2021)
  • Author(s): Shigemitsu Hajime、Kawakami Kosei、Nagata Yuuya、Kajiwara Rikuo、Yamada Shintaro、Mori Tadashi、Kida Toshiyuki
  • Journal Title: Angewandte Chemie International Edition Volume: 61
  • DOI: 10.1002/anie.202114700
  • Peer Reviewed / Open Access
• [Journal Article] Overtemperature-protection intelligent molecular chiroptical photoswitches (2021)
  • Author(s): Yao Jiabin、Wu Wanhua、Xiao Chao、Su Dan、Zhong Zhihui、Mori Tadashi、Yang Cheng
  • Journal Title: Nature Communications Volume: 12 Pages: 2600-2600
  • DOI: 10.1038/s41467-021-22880-z
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Synthesis, Structure, and Chiroptical Properties of Indolo‐ and Pyridopyrrolo‐Carbazole‐Based C2‐Symmetric Azahelicenes (2021)
  • Author(s): T. Taniguchi, U. Nishii, T. Mori, K. Nakayama, M. Miura
  • Journal Title: Chemistry-A European Journal Volume: 27 Pages: 1-7
  • DOI: 10.1002/chem.202100327
  • Peer Reviewed
• [Journal Article] A cyanine dye based supramolecular photosensitizer enabling visible-light-driven organic reaction in water (2021)
  • Author(s): Shigemitsu Hajime、Tamemoto Tomoe、Ohkubo Kei、Mori Tadashi、Osakada Yasuko、Fujitsuka Mamoru、Kida Toshiyuki
  • Journal Title: Chemical Communications Volume: 57 Pages: 11217-11220
  • DOI: 10.1039/d1cc04685c
  • Peer Reviewed / Open Access
• [Journal Article] Chiroptical Properties of Symmetric Double, Triple, and Multiple Helicenes (2021)
  • Author(s): Mori Tadashi
  • Journal Title: Chemical Reviews Volume: 121 Pages: 2373-2412
  • DOI: 10.1021/acs.chemrev.0c01017
  • Peer Reviewed / Open Access
• [Journal Article] Irreverent Nature of Dissymmetry Factor and Quantum Yield in Circularly Polarized Luminescence of Small Organic Molecules (2021)
  • Author(s): Nagata Yuya、Mori Tadashi
  • Journal Title: Frontiers in Chemistry Volume: 8 Pages: 448-448
  • DOI: 10.3389/fchem.2020.00448
  • Peer Reviewed / Open Access
• [Journal Article] Relevance of the Entropy Factor in Stereoselectivity Control of Asymmetric Photoreactions (2021)
  • Author(s): Mori Tadashi
  • Journal Title: Synlett Volume: 31 Pages: 1259-1267
  • DOI: 10.1055/s-0040-1707962
  • Peer Reviewed
• [Journal Article] Enantiodifferentiating Photodimerization of a 2,6-Disubstituted Anthracene Assisted by Supramolecular Double-Helix Formation with Chiral Amines (2020)
  • Author(s): A. Urushima, D. Taura, M. Tanaka, N. Horimoto, J. Tanabe, N. Ousaka, T. Mori, E. Yashima
  • Journal Title: Angewandte Chemie International Edition Volume: 59 Pages: 7478-7486
  • DOI: 10.1002/anie.201916103
  • Peer Reviewed
• [Journal Article] Combined Experimental and Theoretical Studies on Planar Chirality of Partially Overlapped C2-Symmetric [3.3](3,9)Dicarbazolophanes (2020)
  • Author(s): Tani Keita、Imafuku Risa、Miyanaga Kanae、Masaki Miyuki Eiraku、Kato Haruka、Hori Kazushige、Kubono Koji、Taneda Masatsugu、Harada Takunori、Goto Kenta、Tani Fumito、Mori Tadashi
  • Journal Title: The Journal of Physical Chemistry A Volume: 124 Pages: 2057-2063
  • DOI: 10.1021/acs.jpca.0c00286
  • Peer Reviewed
• [Journal Article] Aggregation-induced photocatalytic activity and efficient photocatalytic hydrogen evolution of amphiphilic rhodamines in water (2020)
  • Author(s): Shigemitsu Hajime、Tani Youhei、Tamemoto Tomoe、Mori Tadashi、Li Xinxi、Osakada Yasuko、Fujitsuka Mamoru、Kida Toshiyuki
  • Journal Title: Chemical Science Volume: 11 Pages: 11843-11848
  • DOI: 10.1039/d0sc04285d
  • Peer Reviewed / Open Access
• [Journal Article] Enhancing Photostability of a Coumarin Dye by Self‐inclusion into a Cyclodextrin Cavity in Aqueous Solution and Living Cells (2020)
  • Author(s): Shigemitsu Hajime、Matsuda Keigo、Mori Tadashi、Nakatsuji Hirotaka、Matsusaki Michiya、Kida Toshiyuki
  • Journal Title: Asian Journal of Organic Chemistry Volume: 9 Pages: 2112-2115
  • DOI: 10.1002/ajoc.202000365
  • Peer Reviewed
• [Journal Article] A Thioxanthone Sensitizer with a Chiral Phosphoric Acid Binding Site: Properties and Applications in Visible Light‐Mediated Cycloadditions (2020)
  • Author(s): Pecho Franziska、Zou You‐Quan、Gram?ller Johannes、Mori Tadashi、Huber Stefan M.、Bauer Andreas、Gschwind Ruth M.、Bach Thorsten
  • Journal Title: Chemistry - A European Journal Volume: 26 Pages: 5190-5194
  • DOI: 10.1002/chem.202000720
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Figure‐eight Octaphyrin Bis‐Ge(IV) Complexes: Synthesis, Structures, Aromaticity, and Chiroptical Properties (2020)
  • Author(s): M. Izawa, T. Suito, S.-i. Ishida, D. Shimizu, T. Tanaka, T. Mori, A. Osuka
  • Journal Title: Chemistry - An Asian Journal Volume: N/A Pages: 1440-1448
  • DOI: 10.1002/asia.202000159
  • Peer Reviewed
• [Journal Article] An Ultimate Stereocontrol in Supramolecular Photochirogenesis: Photocyclodimerization of 2-Anthracenecarboxylate Mediated by Sulfur-Linked β-Cyclodextrin Dimers (2019)
  • Author(s): Ji Jiecheng、Wu Wanhua、Liang Wenting、Cheng Guo、Matsushita Ryohei、Yan Zhiqiang、Wei Xueqin、Rao Ming、Yuan De-Qi、Fukuhara Gaku、Mori Tadashi、Inoue Yoshihisa、Yang Cheng
  • Journal Title: J. Am. Chem. Soc. Volume: 141 Pages: 9225-9238
  • DOI: 10.1021/jacs.9b01993
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Diastereoselective photocycloaddition reaction of vinyl ether tethered to 1,4-naphthoquinone (2019)
  • Author(s): Hiroki Ishikawa, Tim Chung, Gaku Fukuhara, Hajime Shigemitsu, Toshiyuki Kida, Thorsten Bach, Tadashi
  • Journal Title: ChemPhotoChem. Volume: 印刷中 Pages: 243-250
  • DOI: 10.1002/cptc.201900022
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Transient Circular Dichroism Measurement of the Excited Triplet State of Pristine Hexahelicene in Solution at Room Temperature (2019)
  • Author(s): Makoto Kuronuma , Takehito Sato , Yasuyuki Araki ,* Tadashi Mori , Seiji Sakamoto, Yoshihisa Inoue , Osamu Ito , and Takehiko Wada
  • Journal Title: Chem. Lett. Volume: 48 Issue: 4 Pages: 357-360
  • DOI: 10.1246/cl.190012
  • NAID: 130007624434
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Sign Control of Circularly Polarized Luminescence Based on Geometric Arrangement of Fluorescent Pyrene Units in a Binaphthyl Scaffold (2019)
  • Author(s): Kaji Daiki、Ikeda Shintaro、Takamura Kenya、Tajima Nobuo、Shizuma Motohiro、Mori Tadashi、Miyasaka Makoto、Imai Yoshitane
  • Journal Title: Chem. Lett. Volume: 48 Issue: 8 Pages: 874-876
  • DOI: 10.1246/cl.190246
  • NAID: 130007687741
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Propeller Chirality (2019)
  • Author(s): Mori Tadashi
  • Journal Title: Kokagaku Volume: 49 Pages: 163-166
  • NAID: 40021760386
  • Peer Reviewed
• [Journal Article] Selective Formation of Helical Tetrapyrrin‐fused Porphyrins by Oxidation of beta‐to‐beta Linked meso‐Aminoporphyrin Dimers (2019)
  • Author(s): Osuka Atsuhiro、Fujimoto Keisuke、Shimizu Daiki、Mori Tadashi、Li Yuanyuan、Zhou Mingbo、Song Jianxin
  • Journal Title: Chem. Eur. J. Volume: 25 Pages: 1711-1715
  • DOI: 10.1002/chem.201805659
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Hydrostatic Pressure on Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes: Explicit Solvent Effects on Differential Volumes in Methylcyclohexane and Hexane (2019)
  • Author(s): Kosaka, T.; Iwai, S.; Fukuhara, G.; Imai, Y.; Mori, T.
  • Journal Title: Chemistry - A European Journal Volume: 25 Pages: 2011-2018
  • DOI: 10.1002/chem.201804688
  • Peer Reviewed
• [Presentation] Organic Asymmetric Photoreactions Controlled by Weak Molecular Interactions (2021)
  • Author(s): Tadashi Mori
  • Organizer: Pacifichem 2021
  • Int'l Joint Research / Invited
• [Presentation] Supramolecular Asymmetric Photochirogenesis (SMAP) of 2-Anthracene Carboxylate and 2,6-Anthracene Dicarboxylate mediated by Serum Albumin as Chiral Reaction Nanoreactor (2021)
  • Author(s): Masaki Nishijima, Nagisa Kawa, Misaki Kawai, Sota Toyooka, Yuta Fujishiro, Tadashi Mori, Yasuyuki Araki, Yoshihisa Inoue, Takehiko Wada
  • Organizer: Materials Research Meeting 2021
  • Int'l Joint Research / Invited
• [Presentation] Rational Design for Small Molecule Circular Dichroisms and Circularly Polarized Luminescence (2021)
  • Author(s): Tadashi Mori
  • Organizer: Materials Research Meeting 2021
  • Int'l Joint Research / Invited
• [Presentation] Organic Photoreactions Controlled by Weak Molecular Interactions (2021)
  • Author(s): Tadashi Mori
  • Organizer: APC2021. 11th Asian Photochemistry Conference
  • Int'l Joint Research / Invited
• [Presentation] キラルルイス酸を用いた1,4-ナフトキノンとアルケンの分子内光環化付加反応 (2020)
  • Author(s): 清水菜生・森 直
  • Organizer: 2020年光化学討論会
• [Presentation] 多環式芳香族化合物を修飾したシクロデキストリン誘導体の円偏光発光特性 (2020)
  • Author(s): 山田慎太郎・重光孟・川上晃聖・森 直・木田敏之
  • Organizer: 2020年光化学討論会
• [Presentation] シクロデキストリン環上でのピレンエキシマー形成による円偏光発光特性の発現 (2020)
  • Author(s): 川上晃聖・重光孟・梶原陸生・森 直・木田敏之
  • Organizer: 2020年光化学討論会
• [Presentation] ヒト血清アルブミンをキラル反応場に用いたアントラセン誘導体の触媒的超分子不斉光反応系の構築 (2020)
  • Author(s): 西嶋政樹・河合美咲・豊岡壮太・藤城祐也・森 直・荒木保幸・井上佳久・和田健彦
  • Organizer: 第14回バイオ関連化学シンポジウム2020
• [Presentation] Is There Any Meaningful Correlation between Emission and Absorption Dissymmetry Factor Values? (2019)
  • Author(s): Tadashi Mori
  • Organizer: Chirality 2019. 31th International Symposium on Chirality
  • Int'l Joint Research / Invited
• [Presentation] Non-Conventional Control of Organic Photoreactions (2019)
  • Author(s): Tadashi Mori
  • Organizer: ICoPP 2019. International Conference on Photocatalysis and Photoenergy 2019
  • Int'l Joint Research / Invited
• [Presentation] Effectual Photon Upconversion through the Toroidal Interaction (2019)
  • Author(s): Tadashi Mori
  • Organizer: Final International Symposium on Photosynergetics, Grant-in-Aid for Scientific Research on Innovative Areas (2014-2018), MEXT, Japan
  • Int'l Joint Research / Invited
• [Presentation] Control of Circular Dichroisms and Circularly Polarized Luminescence Responses in Small Organic Molecules (2019)
  • Author(s): Tadashi Mori
  • Organizer: Green 2019. The 5th Global Research Efforts On Energy And Nanomaterials
  • Int'l Joint Research / Invited
• [Book] Circularly Polarized Luminescence of Isolated Small Organic Molecules (2020)
  • Author(s): Mori, Tadashi
  • Total Pages: 342
  • Publisher: Springer
  • ISBN: 9789811523090