Effectual Photon Upconversion through the Toroidal Interaction

• Project Area: Application of Cooperative-Excitation into Innovative Molecular Systems with High-Order Photo-functions
• Project/Area Number: 17H05261
• 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): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2018: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2017: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: エネルギー移動 / フォトンアップコンバージョン / トロイダル相互作用 / 三重項三重項対消滅 / キラリティー / ジフェニルアントラセン / プロペラ構造 / ヘキサ アリールベンゼン / アップコンバージョン / 三重項対消滅 / ヘキサアリールベンゼン

Outline of Annual Research Achievements

本研究では、三重項三重項対消滅を利用したフォトンアップコンバージョンの効率化における新しい分子設計指針を提唱することが目的である。具体的には、ヘキサアリールベンゼンの特異なトロイダル相互作用に着目し、プロペラ状の形状の羽にあたる位置に、ジフェニルアントラセン骨格を導入することで、効率的なエネルギー移動、エネルギーマイグレーションを誘起し、三重項励起状態の高寿命化、効率的なアップコンバージョンを達成することが可能かどうか実証することが課題となる。研究の初年度において、ジフェニルアントラセンを6つ導入したヘキサアリールベンゼン誘導体の合成を試みたところ、合成法の確立には至ったが溶解度の問題から精製が困難であり、厳密な物性評価を行うことはできなかった。
本年度は、溶解度の向上が見込まれる長鎖アルキル基を導入した誘導体を新たに設計し、合成した。初期的な分光学的測定により、すでに期待通り高いアップコンバージョンが観測されることが明らかとなっているが、今後の課題としては合成のスケールアップを進め、各過程の詳細な物性評価を進めていく必要がある。
キラルなヘキサアリールベンゼンのプロペラキラリティーに関しては、その動的挙動などに関して検討を進め、掲載雑誌の表紙にも採用されるなど注目を集めている。また、一連の研究に関して、本の執筆と編集（シュプリンガー社より出版予定）も進めているところである。関連する成果などは合わせて15報の論文として発表することができた。成果は、国内外の学会等でも発表し、積極的な広報活動にも努めた。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30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] 四川大学/中国薬科大学(中国)
• [Int'l Joint Research] ヨンセイ大学(韓国)
• [Int'l Joint Research] ウプサラ大学(スウェーデン)
• [Int'l Joint Research] タリン工科大学(エストニア)
• [Int'l Joint Research] チェコ科学アカデミー(チェコ)
• [Int'l Joint Research]
• [Journal Article] Combined Experimental and Theoretical Study on Circular Dichroism and Circularly Polarized Luminescence of Configurationally Robust D3-Symmetric Triple Pentahelicene (2018)
  • Author(s): Tanaka Hiroki、Kato Yuka、Fujiki Michiya、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: The Journal of Physical Chemistry A Volume: 122 Issue: 37 Pages: 7378-7384
  • DOI: 10.1021/acs.jpca.8b05247
  • Peer Reviewed
• [Journal Article] Cover Feature: Circularly Polarized Luminescence and Circular Dichroisms in Small Organic Molecules: Correlation between Excitation and Emission Dissymmetry Factors (ChemPhotoChem 5/2018) (2018)
  • Author(s): Tanaka Hiroki、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: ChemPhotoChem Volume: 2 Issue: 5 Pages: 383-383
  • DOI: 10.1002/cptc.201800093
  • Peer Reviewed
• [Journal Article] Circularly Polarized Luminescence and Circular Dichroisms in Small Organic Molecules: Correlation between Excitation and Emission Dissymmetry Factors (2018)
  • Author(s): Tanaka Hiroki、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: ChemPhotoChem Volume: 2 Issue: 5 Pages: 386-402
  • DOI: 10.1002/cptc.201800015
  • Peer Reviewed
• [Journal Article] Symmetry-based rational design for boosting chiroptical responses (2018)
  • Author(s): Tanaka Hiroki、Ikenosako Mina、Kato Yuka、Fujiki Michiya、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: Communications Chemistry Volume: 1 Issue: 1 Pages: 38-38
  • DOI: 10.1038/s42004-018-0035-x
  • Peer Reviewed / Open Access
• [Journal Article] Spiroborate-Based Double-Stranded Helicates: Meso-to-Racemo Isomerization and Ion-Triggered Springlike Motion of the Racemo-Helicate (2018)
  • Author(s): Ousaka Naoki、Shimizu Kaori、Suzuki Yoshimasa、Iwata Takuya、Itakura Manabu、Taura Daisuke、Iida Hiroki、Furusho Yoshio、Mori Tadashi、Yashima Eiji
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 49 Pages: 17027-17039
  • DOI: 10.1021/jacs.8b08268
  • Peer Reviewed
• [Journal Article] Entropy-Driven Diastereoselectivity Improvement in the Paterno-Buchi Reaction of 1-Naphthyl Aryl Ethenes with a Chiral Cyanobenzoate through Remote Alkylation (2018)
  • Author(s): Nagasaki Keisuke、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 18 Pages: 4880-4885
  • DOI: 10.1002/anie.201801330
  • Peer Reviewed
• [Journal Article] Solvent and Temperature Effects on Dynamics and Chiroptical Properties of Propeller Chirality and Toroidal Interaction of Hexaarylbenzenes (2018)
  • Author(s): Kosaka Tomoyo、Iwai Satono、Inoue Yoshihisa、Moriuchi Toshiyuki、Mori Tadashi
  • Journal Title: The Journal of Physical Chemistry A Volume: 122 Issue: 37 Pages: 7455-7463
  • DOI: 10.1021/acs.jpca.8b06535
  • Peer Reviewed
• [Journal Article] 1,8-Diphenyl-9,10-Bis(arylethynyl)phenanthrenes: Synthesis, Distorted Structure, and Optical Properties (2018)
  • Author(s): Konishi Akihito、Morinaga Atsushi、Fukuhara Gaku、Nishijima Masaki、Mori Tadashi、Kida Toshiyuki、Yasuda Makoto
  • Journal Title: Chemistry A European Journal Volume: 印刷中 Issue: 25 Pages: 6625-6631
  • DOI: 10.1002/chem.201800150
  • Peer Reviewed / Open Access
• [Journal Article] A BODIPY-based near infrared fluorescent probe for Fe3+ in water (2018)
  • Author(s): Ji Jiecheng、Chereddy Syama Sundar、Ren Yi、Chen Xingming、Su Dan、Zhong Zhihui、Mori Tadashi、Inoue Yoshihisa、Wu Wanhua、Yang Cheng
  • Journal Title: Journal of Photochemistry and Photobiology A: Chemistry Volume: 355 Pages: 78-83
  • DOI: 10.1016/j.jphotochem.2017.10.043
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Significant Enhancement of Absorption and Luminescence Dissymmetry Factors in the Far-Red Region: A Zinc(II) Homoleptic Helicate Formed by a Pair of Achiral Dipyrromethene Ligands (2018)
  • Author(s): Ito Hiroaki、Sakai Hayato、Okayasu Yoshinori、Yuasa Junpei、Mori Tadashi、Hasobe Taku
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 63 Pages: 16889-16894
  • DOI: 10.1002/chem.201804171
  • Peer Reviewed
• [Journal Article] Synthesis, Structures, and Optical Properties of Azahelicene Derivatives and Unexpected Formation of Azahepta[8]circulenes (2018)
  • Author(s): Fengkun Chen, Takayuki Tanaka, Tadashi Mori, and Atsuhiro Osuka
  • Journal Title: Chemistry A European Journal, Volume: N/A Issue: 29 Pages: 7489-7497
  • DOI: 10.1002/chem.201800617
  • Peer Reviewed / Open Access
• [Journal Article] Preface for special issue on photosynergetics (2018)
  • Author(s): Biju Vasudevanpillai、Mori Tadashi、Asahi Tsuyoshi、Miyasaka Hiroshi
  • Journal Title: Journal of Photochemistry and Photobiology C: Photochemistry Reviews Volume: 34 Pages: 1-1
  • DOI: 10.1016/j.jphotochemrev.2018.02.003
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Porphyrin-Based Air-Stable Helical Radicals (2017)
  • Author(s): Kato Kenichi、Furukawa Ko、Mori Tadashi、Osuka Atsuhiro
  • Journal Title: Chem. Eur. J. Volume: 24 Issue: 3 Pages: 572-575
  • DOI: 10.1002/chem.201705291
  • Peer Reviewed / Open Access
• [Journal Article] Temperature-Driven Planar Chirality Switching of a Pillar[5]arene-Based Molecular Universal Joint (2017)
  • Author(s): Yao Jiabin、Wu Wanhua、Liang Wenting、Feng Yujun、Zhou Dayang、Chruma Jason J.、Fukuhara Gaku、Mori Tadashi、Inoue Yoshihisa、Yang Cheng
  • Journal Title: Angew. Chem. Int. Ed. Volume: 56 Issue: 24 Pages: 6869-6873
  • DOI: 10.1002/anie.201702542
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Energetics of Baird aromaticity supported by inversion of photoexcited chiral [4n]annulene derivatives (2017)
  • Author(s): Ueda Michihisa、Jorner Kjell、Sung Young Mo、Mori Tadashi、Xiao Qi、Kim Dongho、Ottosson Henrik、Aida Takuzo、Itoh Yoshimitsu
  • Journal Title: Nat. Commun. Volume: 8 Issue: 1 Pages: 346-346
  • DOI: 10.1038/s41467-017-00382-1
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Chiroptical properties of dithia[3.3]cyclophanes composed of anthracene and pyridine/pyridinium moieties: A combined experimental and theoretical study (2017)
  • Author(s): Shimizu Akinori、Nagasaki Keisuke、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: Chirality Volume: 29 Issue: 11 Pages: 677-683
  • DOI: 10.1002/chir.22740
  • Peer Reviewed
• [Journal Article] A Combined Experimental and Theoretical Study on the Circular Dichroism of Staggered and Eclipsed Forms of Dimethoxy[2.2]-, [3.2]-, and [3.3]Pyridinophanes and Their Protonated Forms (2017)
  • Author(s): Shimizu Akinori、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: J. Phys. Chem. A Volume: 121 Issue: 44 Pages: 8389-8398
  • DOI: 10.1021/acs.jpca.7b08623
  • Peer Reviewed
• [Journal Article] Sui Generis Helicene-Based Supramolecular Chirogenic System: Enantioselective Sensing, Solvent Control, and Application in Chiral Group Transfer Reaction (2017)
  • Author(s): Hasan Mohammed、Khose Vaibhav N.、Mori Tadashi、Borovkov Victor、Karnik Anil V.
  • Journal Title: ACS Omega Volume: 2 Issue: 2 Pages: 592-598
  • DOI: 10.1021/acsomega.6b00522
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Oligosaccharide Sensing in Aqueous Media by Porphyrin-Curdlan Conjugates: A Prt-Porter Rather Than Haute-Couture Approach (2017)
  • Author(s): Fukuhara Gaku、Sasaki Mayuko、Numata Munenori、Mori Tadashi、Inoue Yoshihisa
  • Journal Title: Chem. Eur. J. Volume: 23 Issue: 47 Pages: 11272-11278
  • DOI: 10.1002/chem.201701360
  • Peer Reviewed
• [Journal Article] Enantioselectivity of 2,2′,3,5′,6-Pentachlorobiphenyl (PCB 95) Atropisomers toward Ryanodine Receptors (RyRs) and Their Influences on Hippocampal Neuronal Networks (2017)
  • Author(s): Feng Wei、Zheng Jing、Robin Galle、Dong Yao、Ichikawa Makoto、Inoue Yoshihisa、Mori Tadashi、Nakano Takeshi、Pessah Isaac N.
  • Journal Title: Environ. Sci. Technol. Volume: 51 Issue: 24 Pages: 14406-14416
  • DOI: 10.1021/acs.est.7b04446
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Closed Pentaaza[9]helicene and Hexathia[9]/[5]helicene: Oxidative Fusion Reactions of ortho-Phenylene Bridged Cyclic Hexapyrroles and Hexathiophenes (2017)
  • Author(s): Fengkun Chen, Takayuki Tanaka, Yong Seok Hong, Tadashi Mori, Dongho Kim, and Atsuhiro Osuka
  • Journal Title: Angewandte Chemie International Edition Volume: 56 Issue: 46 Pages: 14688-14693
  • DOI: 10.1002/anie.201708429
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Intense redox-driven chiroptical switching with a 580 mV hysteresis actuated through reversible dimerization of an azoniahelicene (2017)
  • Author(s): Brandt Jochen R.、Pospil Lubomr、Bednrov Lucie、da Costa Rosenildo Correa、White Andrew J. P.、Mori Tadashi、Tepl Filip、Fuchter Matthew J.
  • Journal Title: Chem. Commun. Volume: 53 Issue: 65 Pages: 9059-9062
  • DOI: 10.1039/c7cc04903j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Asymmetric Photochemical Synthesis Based on Selective Excitation of Charge-Transfer Complexes (2017)
  • Author(s): Mori Tadashi
  • Journal Title: J. Synth. Org. Chem., Jpn. Volume: 75 Pages: 144-152
  • NAID: 130005549270
  • Peer Reviewed
• [Journal Article] Absolute configuration determination through the unique intramolecular excitonic coupling in the circular dichroisms of o,p′-DDT and o,p′-DDD. A combined experimental and theoretical study (2017)
  • Author(s): Tanaka Hiroki、Inoue Yoshihisa、Nakano Takeshi、Mori Tadashi
  • Journal Title: Photochem. Photobiol. Sci. Volume: 16 Issue: 4 Pages: 606-610
  • DOI: 10.1039/c6pp00438e
  • Peer Reviewed
• [Journal Article] Moebius Aromatic [28]Hexaphyrin Ge(IV) and Sn(IV) Complexes: Efficient Formation of Triplet Exited States (2017)
  • Author(s): Mondo Izawa, Taeyeon Kim, Shin-ichiro Ishida, Takayuki Tanaka, Tadashi Mori, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Angewandte Chemie International Edition Volume: 23 Issue: 14 Pages: 3982-3986
  • DOI: 10.1002/anie.201700063
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Propeller Chirality of Boron Heptaaryldipyrromethene: Unprecedented Supramolecular Dimerization and Chiroptical Properties (2017)
  • Author(s): Toyoda Masataka、Imai Yoshitane、Mori Tadashi
  • Journal Title: J. Phys. Chem. Lett. Volume: 8 Issue: 1 Pages: 42-48
  • DOI: 10.1021/acs.jpclett.6b02492
  • Peer Reviewed
• [Journal Article] Protonation-Induced Sign Inversion of the Cotton Effects of Pyridinophanes. A Combined Experimental and Theoretical Study (2017)
  • Author(s): Shimizu Akinori、Inoue Yoshihisa、Mori Tadashi
  • Journal Title: J. Phys. Chem. A Volume: 121 Issue: 5 Pages: 977-985
  • DOI: 10.1021/acs.jpca.6b12287
  • Peer Reviewed
• [Journal Article] Chiral Photochemistry of Charge Transfer Complexes: Effect of Excitation Wavelength (2017)
  • Author(s): Mori Tadashi
  • Journal Title: Symmetry: Culture and Science Volume: 28 Pages: 207-210
  • Peer Reviewed
• [Presentation] Ring Inversion Kinetics of Photoexcited Chiral [4n]Annulene Derivatives: Energetic Impact of Baird Aromaticity (2018)
  • Author(s): Yoshimitsu Itoh, Michihisa Ueda, Kjell Jorner, Young Mo Sung, Tadashi Mori, Qi Xiao1, Dongho Kim, Henrik Ottosson, Takuzo Aida
  • Organizer: ICPOC24. IUPAC International Conference on Physical Organic Chemistry
  • Int'l Joint Research
• [Presentation] Nontrivial Supramolecular Control of Organic Photoreactions (2018)
  • Author(s): Tadashi Mori
  • Organizer: Lecture Conference on Photochemistry
  • Int'l Joint Research / Invited
• [Presentation] Chiral Hexaarylbenzenes for Rathore Memorial (2018)
  • Author(s): Tadashi Mori
  • Organizer: Rathore Memorial Symposium
  • Int'l Joint Research / Invited
• [Presentation] Chirality and Weak Interactions (2018)
  • Author(s): Tadashi Mori
  • Organizer: Department Seminar at Technische Universitaet Muenchen
  • Int'l Joint Research / Invited
• [Presentation] Exploitation of Chiral Photochemistry Utilizing Charge-Transfer Interaction (2018)
  • Author(s): Tadashi Mori
  • Organizer: 2018年光化学討論会
  • Invited
• [Presentation] Effect of Toroidal Interaction on Photon Upconversion through the Triplet-Triplet Annihilation in Hexaarylbenzene Derivatives (2017)
  • Author(s): Makoto Ichikawa, Tomoyo Kosaka, Masataka Toyoda, Tadashi Mori
  • Organizer: Artificial Photosynthesis: Faraday Discussion
  • Int'l Joint Research
• [Presentation] A Combined Experimental and Theoretical Study on Propeller Chirality of Heptaaryldipyrromethenes and Hexaarylbenzenes (2017)
  • Author(s): Masataka Toyoda, Tomoyo Kosaka, Yoshihisa Inoue, Yoshitane Imai, Tadashi Mori
  • Organizer: CD2017. 16th International Conference on Chiroptical Spectroscopy
  • Int'l Joint Research / Invited
• [Presentation] Chirality and Photochemistry (2017)
  • Author(s): Tadashi Mori
  • Organizer: Department Seminar (Universite de Reims)
  • Int'l Joint Research / Invited
• [Presentation] Supramolecular Control of Chiroptical Properties and Toroidal Interaction in Boron Heptaaryldipyrromethenes and Hexaarylbenzenes (2017)
  • Author(s): Tadashi Mori
  • Organizer: Chirality 2017. The 29th International Symposium on Chiral Discrimination
  • Int'l Joint Research / Invited
• [Presentation] Experimental and Theoretical Studies on Propeller Chirality and Toroidal Interaction in Heptaaryldipyrromethenes and Hexaarylbenzenes (2017)
  • Author(s): Tadashi Mori, Masataka Toyoda, Tomoyo Kosaak, Yoshihisa Inoue, Yoshitane Imai
  • Organizer: ICP2017. The 28th International Conference on Photochemistry
  • Int'l Joint Research / Invited
• [Presentation] 特別企画－趣旨説明（ルミネッセンス化学アンサンブル：キラリティーと発光の融合による化学の新潮流） (2017)
  • Author(s): 森 直
  • Organizer: 日本化学会第97春季年会(2017)
• [Presentation] 分子認識を志向したプロペラキラリティーの化学 (2017)
  • Author(s): 森 直
  • Organizer: 2017年度分子無機化学セミナーMICS
  • Invited
• [Book] 光化学フロンティア (2018)
  • Author(s): 森 直（編集：水野 一彦、宮坂 博、池田 浩）
  • Total Pages: 17
  • Publisher: 化学同人
  • ISBN: 9784759814194