高次π空間の創発と機能開発

2013 Fiscal Year Annual Research Report

• Project Area: Emergence of highly elaborated pai-space and its function
• Project/Area Number: 20108001
• Research Institution: Tokyo Gakugei University
• Principal Investigator: 赤阪 健 東京学芸大学, 教育学部, 研究員 (60089810)
• Co-Investigator(Kenkyū-buntansha): 櫻井 英博 分子科学研究所, 大学共同利用機関等の部局等, 准教授 (00262147) ; 安蘇 芳雄 大阪大学, 産業科学研究所, 教授 (60151065)
• Project Period (FY): 2008-11-13 – 2014-03-31
• Keywords: π空間 / 高次π空間 / 創発 / π電子 / 非平面π電子系 / 電子、光、磁気的相互作用 / 機能開発 / 集積化

Research Abstract

本新学術研究領域ではπ電子を持つ化合物に対し、電子や磁場等の影響や、別の化合物が相互作用する状況下において、より広がりを持った、あるいは特徴が変わった、そして究極的には高度で複雑な秩序やシステムまでもが生じる場を「高次π空間」と定義し、この機能、物性、構造および反応機構を明らかにすることを目標とした。四つの研究項目を設定し、項目間での緊密な連携のもとに研究を行ってきた。研究項目A01は「非平面」を切り口に新しいπ電子系の創製を行い、A02はπ電子系の集積化による機能性「高次π空間」の開発を行い、A03では高次π空間にはたらく電子、光、磁気的相互作用を明らかにしながら革新的機能の開発を行ってきた。A04では高次π空間を有する生体分子とタンパク質あるいは他の化合物との相互作用を研究することで新概念の構築を図ってきた。本研究ではこれまでの研究成果を取りまとめることを目的とした。これまでの研究成果の取りまとめを、各研究項目A01～A04で行うと共に、研究項目内および研究項目間での総合的な取りまとめ活動を、本申請研究組織（新学術領域総括班）が中心となって行った。このようにして取りまとめた研究成果を、「研究成果報告書」の冊子体作成ならびに「公開シンポジウム」の開催にて公表した。本新学術領域での研究成果を報告するのみならず、｢高次π空間の創発と機能開発｣の研究をどのように進展させてきたか、今後どのように展開させて行くべきか等をまとめ、今後の若手研究者、大学院生への指針を提示するとともに、周辺の関連分野の研究者に「高次π空間」の魅力を示した。

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] An Improbable Monometallic Cluster Entrapped in a Popular Fullerene Cage: YCN@Cs(6)-C82 (2013)
  • Author(s): Yang, S.; Chen, C.; Liu, F.; Xie, Y.; Li, F.; Jiao, M.; Suzuki, M.; Wei, T.; Wang, S.; Chen, Z.; Lu, X.; Akasaka, T.
  • Journal Title: Scientific Reports Volume: 3 Pages: 1487-1492
  • DOI: 10.1038/spep01487
  • Peer Reviewed
• [Journal Article] Molecular Structure and Chemical Property of a Divalent Metallofullerene Yb@C2(13)-C84 (2013)
  • Author(s): Zhang, W.; Suzuki, M.; Xie, Y.; Bao, L.; Cai, W.; Slanina, Z.; Nagase, S.; Xu, M.; Akasaka, T.; Lu
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Pages: 12730-12735
  • DOI: 10.1021/ja405223t
  • Peer Reviewed
• [Journal Article] A Metallofullerene Electron Donor that Powers an Efficient Spin Flip in a Linear Electron Donor Acceptor Conjugate (2013)
  • Author(s): Rudolf, M.; Feng, L.; Slanina, Z.; Akasaka, T.; Nagase, S.; Guldi, D.
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Pages: 11165-11174
  • DOI: 10.1021/ja403763e
  • Peer Reviewed
• [Journal Article] Helicity Selective Photoreaction of Single-walled Carbon Nanotubes with Organosulfur Compounds in the Presence of Oxygen (2013)
  • Author(s): Maeda, Y.; Higo, J.; Amagai, Y.; Matsui, J.; Ohkubo, K.; Yoshigoe, Y.; Hashimoto, M.; Eguchi, K.; Yamada, M.; Hasegawa, T.; Sato, Y.; Zhou, J.; Lu, J.; Miyashita, T.; Fukuzumi, S.; Murakami, T.; Tohji, K.; Nagase, S; Akasaka, T.
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Pages: 6356-6362
  • DOI: 10.1021/ja402199n
  • Peer Reviewed
• [Journal Article] Mechanistic Study of the Diels-Alder Reaction of Paramagnetic Endohedral Metallofullerene: Reaction of La@C82 with 1,2,3,4,5-Pentamethylcyclopentadiene (2013)
  • Author(s): Sato, S.; Maeda, Y.; Guo, J. -D.; Yamada, M.; Mizorogi, N.; Nagase, S.; Akasaka, T.
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Pages: 5582-5587
  • DOI: 10.1021/ja309763f
  • Peer Reviewed
• [Journal Article] Highly Regioselective Addition of Admantylidene Carbene to Yb@C2v(3)-C80 Affords the First Derivative of Divalent Metallofullerenes (2013)
  • Author(s): Xie, Y.; Suzuki, M.; Cai, W.; Mizorogi, N.; Nagase, S.; Akasaka, T.; Lu, X.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 52 Pages: 5142-5145
  • DOI: 10.1002/anie.201210164
  • Peer Reviewed
• [Journal Article] Intramolecular versus Intermolecular Electronic Interactions between [5,6]-open and [6,6]-closed C60 Adducts with exTTF (2013)
  • Author(s): Takano, Y.; Schubert, C.; Mizorogi, N.; Feng, L.; Iwano, A.; Katayama, M.; Herranz, M. A.; Guldi, D.; Martin, N.; Nagase, S.; Akasaka, T.
  • Journal Title: Chem. Sci. Volume: 4 Pages: 3166-3171
  • DOI: 10.1039/C3SC00004D
  • Peer Reviewed
• [Journal Article] La2@Cs(17490)-C76: A New non-IPR Dimetallic Metallofullerene Featuring Unexpectedly Weak Metal?Pentalene Interactions (2013)
  • Author(s): Suzuki, M.; Mizorogi, N.; Yang, T.; Uhlik, F.; Slanina, Z.; Zhao, X.; Yamada, M.; Maeda, Y.; Hasegawa, T.; Nagase, S.; Lu, X.; Akasaka, T.
  • Journal Title: Chem. Eur. J. Volume: 19 Pages: 17125-17130
  • DOI: 10.1002/chem.201302821
  • Peer Reviewed
• [Journal Article] Electrochemical and Magnetic Properties of a Surface-grafted Novel Endohedral Metallofullerene Derivative (2013)
  • Author(s): Crivillers, N.; Takano, Y.; Matsumoto, Y.; Casado-Montenegro, J.; Mas-Torrent, M.; Rovira, C.; Akasaka, T.; Veciana, J.
  • Journal Title: Chem. Commun. Volume: 49 Pages: 8145-8147
  • DOI: 10.1039/C3CC43578D
  • Peer Reviewed
• [Journal Article] X-Ray Observation of a Helium Atom and Placing a Nitrogen Atom inside He@C60 and He@C70 (2013)
  • Author(s): Morinaka, Y.; Sato, S.; Wakamiya, A.; Nikawa, H.; Mizorogi, N.; Tanabe, F.; Murata, M.; Komatsu, K.; Furukawa, K.; Kato, T.; Nagase, S.; Akasaka, T.; Murata, Y.
  • Journal Title: Nature Commun. Volume: 4 Pages: 1554/1-1554/5
  • DOI: 10.1038/ncomms2574
  • Peer Reviewed
• [Journal Article] Application of MCD Spectroscopy and TD-DFT to Endohedral Metallofullerenes for Characterization of Their Electronic Transitions (2013)
  • Author(s): Yamada, M.; Slanina, Z.; Mizorogi, N.; Muranaka, A.; Maeda, Y.; Nagase, S.; Akasaka, T.; Kobayashi, N.
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 15 Pages: 3593-3601
  • DOI: 10.1039/c3cp44096f
  • Peer Reviewed
• [Journal Article] Coordinative Interactions between Porphyrins and C60, La@C82, and La2@C80 (2013)
  • Author(s): Tsuchiya, T.; Rudolf, M.; Wolfrum, S.; Radhakrishnan, S. G.; Aoyama, R.; Yokosawa, Y.; Oshima, A.; Akasaka, T.; Nagase, S.; Guldi, D. M.
  • Journal Title: Chem. Eur. J. Volume: 19 Pages: 558-565
  • DOI: 10.1002/chem.201202661
  • Peer Reviewed
• [Journal Article] Mapping the Metal Positions inside Spherical C80 Cages: Crystallographic and Theoretical studies of Ce2@D5h-C80 and Ce2@Ih-C80 (2013)
  • Author(s): Feng, L.; Suzuki, M.; Mizorogi, N.; Xing, L.; Yamada, M.; Akasaka, T.; Nagase, S.
  • Journal Title: Chem. Eur. J. Volume: 19 Pages: 988-993
  • DOI: 10.1002/chem.201202341
  • Peer Reviewed
• [Journal Article] The Synthesis of Hexaflorosumanene and its Congeners (2013)
  • Author(s): T. Kojima, M. Kawano, D. Lentz, H. Sakurai
  • Journal Title: Chem. Eur. J. Volume: 19 Pages: 3282-3286
  • DOI: 10.1002/chem.201204622
  • Peer Reviewed
• [Journal Article] Synthesis of Substituted Sumanenes by Aromatic Electrophilic Substitution Reactions (2013)
  • Author(s): B. B. Shrestha, S. Karanjit, G. Panda, S. Higashibayashi, H. Sakurai
  • Journal Title: Chem. Lett. Volume: 42 Pages: 386-388
  • DOI: 10.1246/cl.2013.386
  • Peer Reviewed
• [Journal Article] Stereoelectronic Effect of Curved Aromatic Structure Favouring the Unexpected Endo Conformation of Benzylic Substituted Sumanene (2013)
  • Author(s): S. Higashibayashi, S. Onogi, H. K. Srivastava, G. N. Sastry, Y.-T. Wu, H. Sakurai
  • Journal Title: Angew. Chem. Int. Ed. Volume: 52 Pages: 7314-7316
  • DOI: 10.1002/anie.201303134
  • Peer Reviewed
• [Journal Article] Jet spectroscopy of buckybowl: Electronic and vibrational structures in the S0 and S1 states of triphenylene and sumanene (2013)
  • Author(s): S. Kunishige, M. Kawabata, M. Baba, T. Yamanaka, Y. Morita, S. Higashibayashi, H. Sakurai
  • Journal Title: J. Chem. Phys. Volume: 139 Pages: 044313-044321
  • DOI: 10.1063/1.4816636
  • Peer Reviewed
• [Journal Article] Sumanenylferrocenes and their solid state self-assembly (2013)
  • Author(s): B. Topolinski, B. M. Schmidt, S. Higashibayashi, H. Sakurai, D. Lentz
  • Journal Title: Dalton Trans. Volume: 42 Pages: 13809-13812
  • DOI: 10.1039/c3dt51569a
  • Peer Reviewed
• [Journal Article] Fluorinated and Trifluoromethylated Corannulenes (2013)
  • Author(s): B. M. Schmidt, B. Topolinski, M. Yamada, S. Higashibayashi, M. Shionoya, H. Sakurai, D. Lentz
  • Journal Title: Chem. Eur. J. Volume: 19 Pages: 13872-13880
  • DOI: 10.1002/chem.201301910
  • Peer Reviewed
• [Journal Article] Beam-induced graphitic carbon cage transformation from sumanene aggregates (2013)
  • Author(s): J-i. Fujita, M. Tachi, K. Murakami, H. Sakurai, Y. Morita, S. Higashibayashi, M. Takeguchi
  • Journal Title: Appl. Phys. Lett. Volume: 104 Pages: 043107-043112
  • DOI: 10.1063/1.4863739
  • Peer Reviewed
• [Journal Article] Low band-gap donor–acceptor copolymers based on dioxocylopenta[c]thiophene derivatives as acceptor units: synthesis, properties, and photovoltaic performances (2013)
  • Author(s): J. Huang, Y. Ie, M. Karakawa, Y. Aso
  • Journal Title: J. Mater. Chem. A Volume: 1 Pages: 15000-15009
  • DOI: 10.1039/c3ta13504g
  • Peer Reviewed
• [Journal Article] Near-Infrared Photovoltaic Performance of Conjugated Polymers Containing Thienoisoindigo Acceptor Units (2013)
  • Author(s): M. Karakawa, Y. Aso
  • Journal Title: Macromol. Chem. Phys. Volume: 214 Pages: 2388-2397
  • DOI: 10.1002/macp.201300426
  • Peer Reviewed
• [Journal Article] Three-dimensional electron-accepting compounds containing perylene bis(dicarboximide)s as n-type organic photovoltaic materials (2013)
  • Author(s): Y. Ie, T. Sakurai, S. Jinnai, M. Karakawa, K. Okuda, S. Mori, Y. Aso
  • Journal Title: Chem. Commun. Volume: 49 Pages: 8386-8388
  • DOI: 10.1039/c3cc43925a
  • Peer Reviewed
• [Journal Article] Narrow-optical-gap p-conjugated small molecules based on terminal isoindigo and thienoisoindigo acceptor units for photovoltaic application (2013)
  • Author(s): M. Karakawa, Y. Aso
  • Journal Title: RSC Adv. Volume: 3 Pages: 16259-16263
  • DOI: 10.1039/c3ra42444h
  • Peer Reviewed
• [Journal Article] Arenedithiocarboxyimide-containing extended π-conjugated systems with high electron affinity (2013)
  • Author(s): Y. Ie, S. Jinnai, M. Nitania, Y. Aso
  • Journal Title: J. Mater. Chem. C Volume: 1 Pages: 5373-5380
  • DOI: 10.1039/c3tc31152j
  • Peer Reviewed
• [Journal Article] Self-Assembling Ary-Naphthalendiimide Derivatives with Nitroxide Radical (2013)
  • Author(s): S. Nakatsuji*, K. Aoki, A. Kojoh, H. Akutsu, J. Yamada, M. Karakawa, Y. Aso
  • Journal Title: Asian J. Org. Chem. Volume: 2 Pages: 164-168
  • DOI: 10.1002/ajoc.201200095
  • Peer Reviewed
• [Journal Article] Energy Level Modulation of HOMO, LUMO, and Band-Gap in Conjugated Polymers for Organic Photovoltaic Applications (2013)
  • Author(s): B.-G. Kim, X. Ma, C. Chen, Y. Ie, E. W. Coir, H. Hashemi, Y. Aso, P. F. Green, J. Kieffer, J. Kim
  • Journal Title: Adv. Funct. Mater. Volume: 23 Pages: 439-445
  • DOI: 10.1002/adfm.201201385
  • Peer Reviewed
• [Presentation] New Vistas in Fullerene Endohedrals (2013)
  • Author(s): Takeshi Akasaka
  • Organizer: The 3 rd Symposium on Carbon Nanoforms
  • Place of Presentation: IMDA-Nanoscience, Madrid, Spain
  • Year and Date: 20130926-20130927
  • Invited
• [Presentation] New Vistas in Fullerene Endohedrals (2013)
  • Author(s): Takeshi Akasaka
  • Organizer: 1st International Symposium on Nanocarbons - Fullerenes, Endofullerenes, Carbon Nanotubes and Carbon Nanostructures
  • Place of Presentation: University of Science and Technology of China, Hefei, China
  • Year and Date: 20130616-20130619
  • Invited
• [Presentation] New Vistas in Fullerene Endohedrals
  • Author(s): Takeshi Akasaka
  • Organizer: Department Lecture, Department of Chemistry
  • Place of Presentation: Xiamen University, Xiamen, China
  • Invited
• [Presentation] New Vistas in Fullerene Endohedrals
  • Author(s): Takeshi Akasaka
  • Organizer: Workshop on Emerging Materials
  • Place of Presentation: University of Trieste, Trieste, Italy
  • Invited
• [Presentation] ナノカーボンを基軸とする高次π空間の創製と機能開拓
  • Author(s): 赤阪 健
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学、名古屋
  • Invited
• [Presentation] Asymmetric Synthesis of C3 Symmetric Buckybowls
  • Author(s): Hidehiro Sakurai
  • Organizer: PERCH-CIC Congress VIII
  • Place of Presentation: Jomtien Palm Beach Hotel & Resort, Pattaya, Thailand
  • Invited
• [Presentation] Synthesis of Sumanene and Related Buckybowls
  • Author(s): Hidehiro Sakurai
  • Organizer: 15th Asian Chemical Congress
  • Place of Presentation: Resort World Sentosa, Singapore
  • Invited
• [Presentation] Substituted Sumanenes: From Fundamental to Applied Research
  • Author(s): Hidehiro Sakurai
  • Organizer: 9th IUPAC International Symposium on Novel Materials and their Synthesis and 23rd International Symposium on Fine Chemistry and Functional Polymers
  • Place of Presentation: Fudan University, Shanghai, China
  • Invited
• [Presentation] バッキーボウル化学におけるキラリティ
  • Author(s): 櫻井英博
  • Organizer: 第５回キラルサイエンス＆テクノロジーシンポジウム
  • Place of Presentation: 早稲田大学、東京
  • Invited
• [Presentation] 精密合成法を基盤とした非平面π共役化合物「バッキーボウル」に関する研究
  • Author(s): 櫻井英博
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学、名古屋
  • Invited
• [Presentation] バッキーボウルの特徴を生かした機能開発へ向けて
  • Author(s): 櫻井英博
  • Organizer: 日本化学会第９４春季年会
  • Place of Presentation: 名古屋大学、名古屋
  • Invited
• [Presentation] Highly Electron-Accepting pi-Conjugated Compounds for Organic Field-Effect Transistor and Photovoltaic Application
  • Author(s): Y. Aso
  • Organizer: The Sixth East Asia Symposium on Functional Dyes and Advanced Materials (EAS-6)
  • Place of Presentation: National Tsing Hua University, Hsinchu, Taiwan
  • Invited
• [Book] 未来材料を創出するπ電子系の科学―新しい合成・構造・機能化、、カレントレビューNo.12 (2013)
  • Author(s): 前田 優、赤阪 健
  • Total Pages: p. 61-69
  • Publisher: 化学同人出版
• [Book] 高次π空間の創発と機能開発 (2013)
  • Author(s): 土屋敬広、溝呂木直美、永瀬 茂、赤阪 健
  • Total Pages: p. 5-9
  • Publisher: シーエムシー出版
• [Book] 高次π空間の創発と機能開発 (2013)
  • Author(s): 櫻井英博
  • Total Pages: pp. 40-43
  • Publisher: シーエムシー出版
• [Book] 未来材料を創出するπ電子系の科学―新しい合成・構造・機能化、カレントレビューNo.12研究 (2013)
  • Author(s): 櫻井英博，東林修平
  • Total Pages: pp. 46-53
  • Publisher: 化学同人出版
• [Book] 高次π空間の創発と機能開発 (2013)
  • Author(s): 安蘇芳雄
  • Total Pages: pp. 10-15
  • Publisher: シーエムシー出版
• [Remarks] 筑波大学生命領域学際研究センター赤阪研究室
  • URL: http://www.tara.tsukuba.ac.jp/~akasaka-lab/
• [Remarks] 分子科学研究所協奏分子システム研究センター機能分子システム創成研究部門櫻井グループ
  • URL: http://groups.ims.ac.jp/organization/sakurai_g/
• [Remarks] 大阪大学産業科学研究所安蘇研究室
  • URL: http://www.sanken.osaka-u.ac.jp/labs/omm/
• [Patent(Industrial Property Rights)] ｎ型半導体化合物、及びｐ型半導体化合物を含有する組成物 (2013)
  • Inventor(s): 安蘇芳雄、家 裕隆、辛川 誠、汪 イー、永井隆文、足達健二
  • Industrial Property Rights Holder: 安蘇芳雄、家 裕隆、辛川 誠、汪 イー、永井隆文、足達健二
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2013-251554
  • Filing Date: 2013-12-04
• [Patent(Industrial Property Rights)] フラーレン誘導体、及びｎ型半導体材料 (2013)
  • Inventor(s): 永井隆文、足達健二、辛川 誠、安蘇芳雄、家 裕隆
  • Industrial Property Rights Holder: 永井隆文、足達健二、辛川 誠、安蘇芳雄、家 裕隆
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2013-181678
  • Filing Date: 2013-09-02
• [Patent(Industrial Property Rights)] フラーレン誘導体、及びｎ型半導体材料 (2013)
  • Inventor(s): 永井隆文、足達健二、辛川 誠、安蘇芳雄、家 裕隆
  • Industrial Property Rights Holder: 永井隆文、足達健二、辛川 誠、安蘇芳雄、家 裕隆
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2013-207724
  • Filing Date: 2013-10-02
• [Patent(Industrial Property Rights)] 共役系化合物，並びにこれを用いた有機薄膜及び有機薄膜素子 (2008)
  • Inventor(s): 家 裕隆，安蘇芳雄，岡部 誠，上田将人
  • Industrial Property Rights Holder: 家 裕隆，安蘇芳雄，岡部 誠，上田将人
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 第5342852号
  • Filing Date: 2008-11-12
  • Acquisition Date: 2013-08-16