エキシプレックス制御キラル光化学

• Project Area: Application of Cooperative-Excitation into Innovative Molecular Systems with High-Order Photo-functions
• Project/Area Number: 15H01087
• 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: Osaka University
• Principal Investigator: 森 直 大阪大学, 工学研究科, 准教授 (70311769)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000); Fiscal Year 2016: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2015: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
• Keywords: 光化学 / 有機化学 / エキシプレックス / 励起CT錯体 / 不斉反応 / 励起状態相互作用 / キロプティカル特性 / 高次励起状態 / 励起ＣＴ錯体 / 不斉合成

Outline of Annual Research Achievements

電子受容体と供与体の光化学において、励起状態での錯体形成、いわゆるエキシプレックスの関与が重要である。しかしながらこれらの化学種は短寿命であり、その構造の精密制御は未だ難しい課題である。本研究では、基底状態での電荷移動（ＣＴ）相互作用を活用し、その電荷移動吸収帯の励起による新しい構造制御の指針を不斉合成法として実証するものである。
本年度は公募研究の２年目の節目の年であったが、研究計画の当初目的はほぼ問題なく達成でき、8件の国際会議等での招待講演を行ったほか、J. Am. Chem. Soc.誌、J. Phys. Chem. Lett.誌を含む計15報の原著論文に報告することができた。成果の一部は、新聞報道もされるなど、特に注目を集めることとなった。また、J. Photochem. Photobiol. A誌のゲストエディターとして特集号を企画、編纂し、その出版にたどり着くことができた。これまでの成果を日本語でまとめ、有機合成化学協会誌に寄稿し、啓発活動にも努めた。これらの成果は、申請者の基盤研究（Ｂ）での成果と協働的に発展しつつあり、さらに次年度、国際共同強化研究として大きく発展させようとしているところである。
一方、領域会議等の交流の中で、本質的に高次複合系を達成するための新たな目標を決定するに至り、次期の公募研究として、特に共同研究として展開するための方向性を決定することができた。このような方向での進展は、目に見える形の成果とは言えないが、今後の研究展開において極めて重要なものであると位置づけており、今後のさらなる発展を期待している。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] マーケット大学/ノースダコタ大学(米国)
• [Int'l Joint Research] ミュンヘン工科大学(ドイツ)
• [Int'l Joint Research] ビクトリア大学(カナダ)
• [Int'l Joint Research] 四川大学(中国)
• [Int'l Joint Research] マーケット大学/ノースダコタ大学(米国)
• [Int'l Joint Research] ミュンヘン工科大学(ドイツ)
• [Int'l Joint Research] ビクトリア大学(カナダ)
• [Journal Article] Optical Activity and Optical Anisotropy in Photomechanical Crystals of Chiral Salicylidenephenylethylamines (2016)
  • Author(s): Takanabe, A.; Tanaka, M.; Johmoto, K.; Uekusa, H.; Mori, T.; Koshima, H.; Asahi, T.
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 45 Pages: 15066-15077
  • DOI: 10.1021/jacs.6b09633
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Long-Lived Triplet Excited States of Bent-Shaped Pentacene Dimers by Intramolecular Singlet Fission (2016)
  • Author(s): T. Sakuma, H. Sakai, Y. Araki, T. Mori, T. Wada, N. V. Tkachenko, T. Hasobe
  • Journal Title: J. Phys. Chem. A Volume: 120 Issue: 11 Pages: 1867-1875
  • DOI: 10.1021/acs.jpca.6b00988
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Highly Enantiodifferentiating Site of Human Serum Albumin for Mediating Photocyclodimerization of 2-Anthracenecarboxylate Elucidated by Site-Specific Inhibition/Quenching with Xenon (2016)
  • Author(s): Nishijima, M.; Pace, T. C. S.; Bohne, C.; Mori, T.; Inoue, Y.; Wada, T.
  • Journal Title: J. Photochem. Photobiol. A Volume: 331 Pages: 89-94
  • DOI: 10.1016/j.jphotochem.2015.12.019
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] J. Phys. Chem. A (2016)
  • Author(s): Mori, T.; Tanaka, T.; Higashino, T.; Yoshida, K.; Osuka, A.
  • Journal Title: Combined Experimental and Theoretical Investigations on Optical Activities of Mobius Aromatic and Mobius Antiaromatic Hexaphyrin Phosphorus Complexes Volume: 120 Issue: 24 Pages: 4241-4248
  • DOI: 10.1021/acs.jpca.6b03978
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Yoshihisa Inoue - A Researcher's Quest for Photochirogenesis (2016)
  • Author(s): Mori, T.; Fukuhara, G.; Wada, T.
  • Journal Title: J. Photochem. Photobiol. A Volume: 331 Pages: 2-7
  • DOI: 10.1016/j.jphotochem.2016.08.006
  • Peer Reviewed
• [Journal Article] The Themed Issue in Honor of Prof. Yoshihisa Inoue for his Contribution on Molecular and Supramolecular Photochemistry (2016)
  • Author(s): Mori, T.; Fukuhara, G.; Wada, T.
  • Journal Title: J. Photochem. Photobiol. A Volume: 331 Pages: 1-1
  • DOI: 10.1016/j.jphotochem.2016.09.029
  • Peer Reviewed
• [Journal Article] Enantioselective [4+4] photodimerization of anthracene-2,6-dicarboxylic acid mediated by a C2-symmetric chiral template (2016)
  • Author(s): Maturi, M. M.; Fukuhara, G.; Tanaka, K.; Kawanami, Y.; Mori, T.; Inoue, Y.*; Bach, T*
  • Journal Title: Chem. Commun. Volume: 52 Issue: 5 Pages: 1032-1035
  • DOI: 10.1039/c5cc09107a
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Orbital Control of Photochemical Rearrangement of 4-Aryl-1,1-dicyano-1-butenes through the Hyperconjugative Substitution on the Linker Chain (2016)
  • Author(s): Matsuki, N.; Inoue, Y.; Mori, T.
  • Journal Title: J. Phys. Chem. Lett. Volume: 7 Issue: 24 Pages: 4957-4961
  • DOI: 10.1021/acs.jpclett.6b02632
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes. Dynamic Domino Inversion Revealed by Combined Experimental and Theoretical Circular Dichroism Studies (2016)
  • Author(s): Kosaka, T.; Inoue, Y.; Mori, T.
  • Journal Title: J. Phys. Chem. Lett. Volume: 7 Issue: 5 Pages: 783-788
  • DOI: 10.1021/acs.jpclett.6b00179
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Dynamic propeller conformation for the unprecedentedly high degree of chiral amplification of supramolecular helices (2016)
  • Author(s): Kim, T.; Mori, T.; Aida, T.; Miyajima, D.
  • Journal Title: Chem. Sci. Volume: 7 Issue: 11 Pages: 6689-6694
  • DOI: 10.1039/c6sc02814d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Supramolecular Photochirogenesis with a Higher-Order Complex: Highly Accelerated Exclusively Head-to-Head Photocyclodimerization of 2-Anthracenecarboxylic Acid via 2:2 Complexation with Prolinol (2016)
  • Author(s): Kawanami, Y.; Katsumata, S.-y.; Nishijima, M.; Fukuhara, G.; Asano, K.; Suzuki, T.; Yang, C.; Nakamura, A.; Mori, T.; Inoue, Y.
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 37 Pages: 12187-12201
  • DOI: 10.1021/jacs.6b05598
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Enhanced Asymmetric Photocycloaddition of Anthracene Tethered to Maleate versus Fumarate through Non-Fluorescent Exciplex Intermediate (2016)
  • Author(s): Ichikawa, M.; Inoue, Y.; Mori, T.
  • Journal Title: J. Photochem. Photobiol. Volume: 331 Pages: 102-109
  • DOI: 10.1016/j.jphotochem.2015.09.001
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Inherently Chiral Azonia[6]helicene-Modified beta-Cyclodextrin: Synthesis, Characterization, and Chirality Sensing of Underivatized Amino Acids in Water (2016)
  • Author(s): Huang, Q.; Jiang, L.; Liang, W.; Gui, J.; Xu, D.; Wu, W.; Nakai, Y.; Nishijima, M.; Fukuhara, G.; Mori, T.; Inoue, Y.*; Yang, C.*
  • Journal Title: J. Org. Chem. Volume: 81 Issue: 8 Pages: 3430-3434
  • DOI: 10.1021/acs.joc.6b00130
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Electrostatically Promoted Dynamic Hybridization of Glucans with Cationic Polythiophene (2016)
  • Author(s): Fukuhara, G.; Imai, M.; Fuentealba, D.; Ishida, Y.; Kurohara, H.; Yang, C.; Mori, T.; Uyama, H.; Bohne, C.; Inoue, Y.
  • Journal Title: Org. Biomol. Chem. Volume: 14 Issue: 41 Pages: 9741-9750
  • DOI: 10.1039/c6ob01353h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Critical Control by Scaffold Flexibility Achieved in Diastereodifferentiating Photocyclodimerization of 2-Anthracenecarboxylate (2016)
  • Author(s): Fukuhara, G.*; Iida, K.; Mori, T.; Inoue, Y.
  • Journal Title: J. Photochem. Photobiol. A: Chem. Volume: なし Pages: 76-83
  • DOI: 10.1016/j.jphotochem.2016.01.016
  • Peer Reviewed
• [Journal Article] A rational strategy for the realization of chain-growth supramolecular polymerization (2015)
  • Author(s): Jiheong Kang, Daigo Miyajima, Tadashi Mori, Yoshihisa Inoue, Yoshimitsu Itoh, Takuzo Aida
  • Journal Title: Science Volume: 347 Issue: 6222 Pages: 646-651
  • DOI: 10.1126/science.aaa4249
  • Peer Reviewed
• [Journal Article] Excited-State Dynamics Achieved Ultimate Stereocontrol of Photocyclodimerization of Anthracenecarboxylates on a Glucose Scaffold (2015)
  • Author(s): G. Fukuhara, K. Iida, Y. Kawanami, H. Tanaka, T. Mori, Y. Inoue
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 47 Pages: 15007-15014
  • DOI: 10.1021/jacs.5b09775
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Helix Sense-Selective Supramolecular Polymerization Seeded by a One-Handed Helical Polymeric Assembly (2015)
  • Author(s): W. Zhang, W. Jin, T. Fukushima, T. Mori, T. Aida
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 43 Pages: 13792-13795
  • DOI: 10.1021/jacs.5b09878
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Metal-Organic Nanotube with Helical and Propeller-Chiral Motifs Composed of a C10-Symmetric Double-Decker Nanoring (2015)
  • Author(s): H. Yamagishi, T. Fukino, D. Hashizume, T. Mori, Y. Inoue, T. Hikima, M. Takata, T. Aida
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 24 Pages: 7628-7631
  • DOI: 10.1021/jacs.5b04386
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] pH-Independent Charge Resonance Mechanism for UV Protective Functions of Shinorine and Related Mycosporine-like Amino Acids (2015)
  • Author(s): K. Matsuyama, J. Matsumoto, S. Yamamoto, K. Nagasaki, Y. Inoue, M. Nishijima, T. Mori
  • Journal Title: J. Phys. Chem. A Volume: 119 Pages: 12722-12729
  • Open Access / Acknowledgement Compliant
• [Journal Article] Nickel(0)/N-Heterocyclic Carbene-Catalyzed Asymmetric [2+2+2] Cycloaddition of Two Enones and an Alkyne: Access to Cyclohexenes with Four Contiguous Stereogenic Centers (2015)
  • Author(s): R. Kumar, H. Tokura, A. Nishimura, T. Mori, Y. Hoshimoto, M. Ohashi, S. Ogoshi
  • Journal Title: Org. Lett. Volume: 17 Issue: 24 Pages: 6018-6021
  • DOI: 10.1021/acs.orglett.5b02983
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Contrasting Behaviour of Exciplex Ensembles in the Diastereodifferentiating Paterno-Buchi Reaction of Chiral Cyanobenzoate with Naphthyl- and Phenylethenes on Direct or Charge-Transfer Excitation (2015)
  • Author(s): K. Nagasaki, Y. Inoue, T. Mori
  • Journal Title: Aust. J. Chem. Volume: 68 Issue: 11 Pages: 1693-1699
  • DOI: 10.1071/ch15404
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Presentation] Propeller Chirality (2016)
  • Author(s): Tadashi Mori
  • Organizer: UK-Japanese Frontiers of Science Symposium 2016
  • Place of Presentation: Chicheley Hall (Milton Keynes, UK)
  • Year and Date: 2016-11-06
  • Int'l Joint Research / Invited
• [Presentation] A Combined Experimental and Theoretical Studies on Circular Dichroisms of Propeller Chirality of Hexaarylbenzenes and Related Molecules (2016)
  • Author(s): Tadashi Mori
  • Organizer: EMN Meeting on Computation and Theory 2016
  • Place of Presentation: South Point Hotel, Casino & Spa (Las Vegas, NV, USA)
  • Year and Date: 2016-10-10
  • Int'l Joint Research / Invited
• [Presentation] Propeller Chirality of Hexaarylbenzenes and Related Molecules (2016)
  • Author(s): Tomoyo Kosaka, Masataka Toyoda, Yoshihisa Inoue, Tadashi Mori
  • Organizer: The 28th International Symposium on Chiral Discrimination (Chirality 2016
  • Place of Presentation: Universitat Heidelberg (Heidelberg, Germany)
  • Year and Date: 2016-07-24
  • Int'l Joint Research / Invited
• [Presentation] Chiral Photochemistry of Charge Transfer Complexes: Effect of Excitation Wavelength (2016)
  • Author(s): Tadashi Mori
  • Organizer: Symmetry Festival 2016
  • Place of Presentation: Technical University Wien (Vienna, Austria)
  • Year and Date: 2016-07-18
  • Int'l Joint Research / Invited
• [Presentation] Exciplex-Controlled Chiral Photochemistry (2016)
  • Author(s): Tadashi Mori
  • Organizer: 1st International Symposium on Photosynergetics, Grant-in-Aid for Scientific Research on Innovative Areas
  • Place of Presentation: Sigma Hall, Toyonaka Campus, Osaka University (Osaka, Japan)
  • Year and Date: 2016-06-02
  • Int'l Joint Research / Invited
• [Presentation] Propeller Chirality of Hexaarylbenzenes and Related Molecules (2016)
  • Author(s): Tomoyo Kosaka, Masataka Toyoda, Yoshihisa Inoue, Tadashi Mori
  • Organizer: Molecular Chirality Asia 201
  • Place of Presentation: Knowledge Capital Congres Convention Center (Osaka, Japan)
  • Year and Date: 2016-04-15
  • Int'l Joint Research / Invited
• [Presentation] Control of Stereochemistry on Photoreactions of Donor-Acceptor Pairs by Excitation Wavelength (2016)
  • Author(s): Tadashi Mori
  • Organizer: 26th IUPAC Symposium on Photochemistry
  • Place of Presentation: Osaka City Central Public Hall (Osaka, Japan)
  • Year and Date: 2016-04-03
• [Presentation] Weak Interactions in Chiral Photochemistry (2016)
  • Author(s): Tadashi Mori
  • Organizer: Pre-symposium of IUPAC Photochemistry 2016 in Hiroshima
  • Place of Presentation: Hiroshima City Bunka Koryu Kaikan (Hiroshima, Japan)
  • Year and Date: 2016-04-01
  • Int'l Joint Research / Invited
• [Presentation] Charge-Transfer Band Excitations in Donor-Acceptor Systems (2015)
  • Author(s): Tadashi Mori
  • Organizer: Pacifichem 2015
  • Place of Presentation: Hilton Hawaiian Village
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] Highly Enantioselective Biocatalytic Enantiodifferentiating Photocyclodimerization of 2,6-Anthracenedicarboxylate Mediated by Human Serum Albumin (2015)
  • Author(s): Masaki Nishijima, Koichiro Tanaka, Gaku Fukuhara, Tadashi Mori, Yoshihisa Inoue
  • Organizer: Pacifichem 2015
  • Place of Presentation: Hawaii Convention Center
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Dynamic Hybridization Mechanisms of Glucans with Water-Soluble Polythiophene (2015)
  • Author(s): Gaku Fukuhara, Mami Imai, Denis Fuentealba, Koichi Tamano, Mayuko Sasaki, Cheng Yang, Tadashi Mori, Uyama Hiroshi, Cornelia Bohne, Yoshihisa Inoue
  • Organizer: Pacifichem 2015
  • Place of Presentation: Hawaii Convention Center
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] A Combined Experimental and Theoretical Studies on Electronic Circular Dichroisms of Dynamic Propeller Chirality of Hexaarylbenzenes (2015)
  • Author(s): Tomoyo Kosaka, Yoshihisa Inoue, Tadashi Mori
  • Organizer: 15th International Conference on Chiroptical Spectroscopy (CD 2015)
  • Place of Presentation: Hokkaido University
  • Year and Date: 2015-08-30
  • Int'l Joint Research / Invited
• [Presentation] Development of High Sensitive and High Time-Resolve Circular Dichroism Detection Method - Toward the Analyses of Supramolecular Chirality and Dynamics - (2015)
  • Author(s): Takehiko Wada, Makoto Kuronuma, Takehito Sato, Yutaka Sano, Seiji Sakamoto, Makoto Murakami, Katsuji Hasegawa, Tadashi Mori, Yoshihisa Inoue, Yasuyuki Araki
  • Organizer: 15th International Conference on Chiroptical Spectroscopy (CD 2015)
  • Place of Presentation: Hokkaido University
  • Year and Date: 2015-08-30
  • Int'l Joint Research
• [Presentation] A Combined Experimental and Theoretical Investigations on Circular Dichroisms of Dynamic Chirality of Hexaarylbenzenes (2015)
  • Author(s): Tadashi Mori
  • Organizer: The 27th International Symposium on Chiral Discrimination (Chirality 2015)
  • Place of Presentation: Boston Park Plaza Hotel
  • Year and Date: 2015-06-28
  • Int'l Joint Research / Invited
• [Presentation] Hybridization Mechanisms of Cationic Polythiophene with Glucans (2015)
  • Author(s): Gaku Fukuhara, Mami Imai, Denis Fuentealba, Koichi Tamano, Mayuko Sasaki, Cheng Yang, Tadashi Mori, Hiroshi Uyama, Cornelia Bohne, Yoshihisa Inoue
  • Organizer: 10th International Symposium on Macrocyclic and Supramolecular Chemistry (ISMSC-2015)
  • Place of Presentation: Strasbourg Palais des congres
  • Year and Date: 2015-06-28
  • Int'l Joint Research
• [Book] 有機合成実験法ハンドブック第2版(二重結合の光異性化によるオレフィン合成) (2015)
  • Author(s): 森 直
  • Publisher: 丸善出版
• [Book] 有機合成実験法ハンドブック第2版(不斉光反応) (2015)
  • Author(s): 森 直
  • Publisher: 丸善出版