Construction and properties of molecular systems inside the π-space

2012 Fiscal Year Final Research Report

• Project Area: Emergence of highly elaborated pai-space and its function
• Project/Area Number: 20108002
• 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: University of Tsukuba
• Principal Investigator: AKASAKA Takeshi 筑波大学, 数理物質系, 教授 (60089810)
• Co-Investigator(Kenkyū-buntansha): TSUCHIYA Takahiro 筑波大学, 数理物質系, 講師 (10375412) ; YAMADA Michio 東京学芸大学, 教育学部, 助教 (00583098)
• Co-Investigator(Renkei-kenkyūsha): NAGASE Shigeru 京都大学, 福井謙一記念研究センター, シニアリサーチャー (30134901) ; MAEDA Yutaka 東京学芸大学, 教育学部, 准教授 (10345324) ; OINUMA Midori 筑波大学, 数理物質系, 講師 (20323256)
• Project Period (FY): 2008 – 2012
• Keywords: フラーレン / 化学修飾 / 集積化 / FET

Research Abstract

Endohedral metallofullerenes have attracted special interest as building blocks of future nanoscale electronic devices and conducting materials because they have low oxidation and reduction potentials. Although the formation of crystals of endohedral Inetallofullerenes renlains difficult, chemical derivatization allows for their efficient crystallization. In this context, we investigated the charge-carrier mobilities of the single crystal of the La@C_<82>Ad derivative.

Research Products

• [Journal Article] An Endohedral Metallofullerene as a Pure Electron Donor: Intramolecular Electron Transfer in Donor-Acceptor Conjugates of La_2@C_<80> and 11,11,12,12-tetracyano-9,10-anthra-p-quinodimetha ne (TCAQ) (2012)
  • Author(s): Y. Takano, S. Obuchi, N. Mizorogi, R. Garcia, M. A. Herranz, M. Rudolf, D. M. Guldi, N. Martln, S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 19401-19408
  • DOI: DOI:10.1021/ja307341g
  • Peer Reviewed
• [Journal Article] Single Crystal X-ray Diffraction Study of Three Yb@C_<82> Isomers Cocrystallized with Ni^<II>(octaethylporphyrin) (2012)
  • Author(s): M. Suzuki, Z. Slanina, N. Mizorogi, X. Lu, S. Nagase, M. M. Olmstead, A. L. Balch, T. Akasaka
  • Journal Title: J. Am. Chem. Soe Volume: 134 Pages: 18772-18778
  • DOI: DOI:10.1021/ja308706d
  • Peer Reviewed
• [Journal Article] Analysis of Functionalization Degree of Single-Walled Carbon Nanotubes Having Various Substituents (2012)
  • Author(s): Y. Maeda, K.Saito, N. Akanlatsu, Y. Chiba, S. Ohno, Y. Okui, M. Yamada, T. Hasegawa, M. Kako, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 18101-18108
  • DOI: DOI:10.1021/ja308969p
  • Peer Reviewed
• [Journal Article] Stabilizing Ion and Radical Ion Pair States in a Paramagnetic Endohedral Metallofullerene and aπ-Extended Tetrathiafulvalene (2012)
  • Author(s): Y. Takano, S. Obuchi, N. Mizorogi, R. Garcia, M. A. Herranz, M. Rudolf, S. Wolfrum, D. M. Guldi, N. Martin,.S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem Volume: 134 Pages: 16103-16106
  • DOI: DOI:10.1021/ja3055386
  • Peer Reviewed
• [Journal Article] Synthesis of a Silylene-Bridged Endohedral Metallofullerene Lu_ 3N@J_h-C_<80> (2012)
  • Author(s): K.Sato, M. Kako, M. Suzuki, N. Mizorogi, T. Tsuchiya, M. Olmstead, A. Balch, T, Akasaka, S., Nagasaki
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 16033-16039
  • DOI: DOI:10.1021/ja3073929
  • Peer Reviewed
• [Journal Article] Exceptional Chemical Properties of Sc@C_<2v>(9)-C_<82> Probed with Adamantylidine Carbene (2012)
  • Author(s): M. Hachiya, H. Nikawa, N. Mizorogi, T. Tsuchiya, X. Lu, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 15550-15555
  • DOI: DOI:10.1021/ja306890x
  • Peer Reviewed
• [Journal Article] A Paradigmatic Change - Linking Fullerenes to Electron Acceptors (2012)
  • Author(s): L. Feng, M. Rudolf, S. Wolfrum, A. Troeger, Z. Slanina, T. Akasaka, S. Akasaka, S Nagase, N. Martin, T. Ameri, C. Brabec, D. Guldi
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 12190-12197
  • DOI: DOI:10.1021/ja3039695
  • Peer Reviewed
• [Journal Article] Tunable Charge-transport Property of Ih-C_<80> Endohedral Metallofullerenes: Investigation of La_2@C_<80>, Sc_3N@C_<80>, and Sc_3C_2@C_<80> (2012)
  • Author(s): S. Sato, S. Seki, G. Luo, M. Suzuki, J. Lu, S. Nagase, T. Akasaka, J
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 11681-11686
  • DOI: DOI:10.1021/ja303660g
  • Peer Reviewed
• [Journal Article] Unexpected Formation of a Sc_3C_2@C_<80> Bisfulleroid Derivative (2012)
  • Author(s): H. Kurihara, Y. Iiduka, Y. Rubin, M. Waelchli, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. kasaka
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 4092-4095
  • DOI: DOI:10.1021/ja300279x
  • Peer Reviewed
• [Journal Article] Chemical Understanding of Carbide Cluster Metallofullerenes: A Case Study on Sc_2C_2@C_<2v>(5)-C_<80> with Complete X-Ray Crystallographic Characterizations (2012)
  • Author(s): H. Kurihara, X. Lu, Y. Iiduka, H. Nikawa, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 134 Pages: 3139-3144
  • DOI: DOI:10.1021/ja210101f
  • Peer Reviewed
• [Journal Article] A Co-Crystal Composed of the Paramagnetic Endohedral Metallofullerene La@C_<82> and Nickel Porphyrin with High Electron Mobility (2012)
  • Author(s): S. Sato, H. Nikawa, S. Seki, L. Wang, G. Luo, J. Lu, M. Haranaka, T. Tsuchiya, S. Nagase, T. Akasaka
  • Journal Title: Angew. Chem. Int. Ed Volume: 51 Pages: 1589-1591
  • DOI: DOI:10.1002/anie.201106912
  • Peer Reviewed
• [Journal Article] X-Ray Structures of Sc2C2@C2n (n=40, 41, 42): In-Depth Understanding of the Core-Shell Interplay in Carbide Cluster Metallofullerenes (2012)
  • Author(s): H. Kurihara, X. Lu, Y. Iiduka, H. Nikawa, M. Hachiya, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nlaga.sg, T. kasaka
  • Journal Title: Inorg. Chem Volume: 51 Pages: 746-750
  • DOI: DOI:10.1021/ic202438u
  • Peer Reviewed
• [Journal Article] Sc_2@C_<3v>(8)-C_<82> vs. Sc_2C_2@C_<3v>(8)-C_<82>: Drastic Effect of C_2 Capture on the Redox Properties of Scandium Metallofullerenes (2012)
  • Author(s): H. Kurihara, X. Lu, Y. Iiduka, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
  • Journal Title: Chem. Commmun Volume: 48 Pages: 1290-1292
  • DOI: DOI:10.1039/c2cc16422a
  • Peer Reviewed
• [Journal Article] Structural Elucidation and Regioselective Functionalization of an Unexplored Carbide Cluster Metallofullerene Sc_2C_2@C_s(6)-C_<82> (2011)
  • Author(s): X. Lu, K. Nakajima, Y. Iiduka, H. Nikawa, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 19553-19558
  • DOI: DOI:10.1021/ja208841w
  • Peer Reviewed
• [Journal Article] Enantioselective Synthesis of Endohedral Metallofullerenes (2011)
  • Author(s): K. Sawai, Y. Takano, M. Izquierdo, S. Filippone, N. Martin, Z. Slanina, N. Mizorogi, M. Waelchli, T. suchiya, T. Akasaka, S. Nagase
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 17746-17752
  • DOI: DOI:10.1021/ja2062727
  • Peer Reviewed
• [Journal Article] Stable Radical Anions Inside Fullerene Cages:Formation of Reversible Electron Transfer Systems (2011)
  • Author(s): T. Tsuchiva, M. Wielopolski, N. Sakuma, N. Mizorogi, T. Akasaka, T. Kato, D. M. Guldi,S. Nagase
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 13280-13283
  • DOI: DOI:10.1021/ja205391v
  • Peer Reviewed
• [Journal Article] Synthesis and Charge-Transfer Chemistry of La_2@I_h-C_<80>/Sc_3N@I_h-C_<80>- Zinc Porphyrin Conjugates: Impact of Endohedral Cluster (2011)
  • Author(s): L. Feng, S. G. Radhakrishnan, N. Mizorogi, Z. Slanina, H. Nikawa, T. Tsuchiya, T. Akasaka, S. Nagase, N. Martin, D. Guldi
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 7608-7618
  • DOI: DOI:10.1021/ja202331r
  • Peer Reviewed
• [Journal Article] Regioselective Bis-functionalization of Endohedral Dimetallofullerene, La_2@C_<80>:Extremal La-La Distance (2011)
  • Author(s): M. O. Ishitsuka, S. Sano, H. Enoki, S. Sato, H. Nikawa, T. Tsuchiya, Z. Slanina, N. Mizorogi, M. T. H. Liu, T. Akasaka, S. Nagase
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 7128-7134
  • DOI: DOI:10.1021/ja200903q
  • Peer Reviewed
• [Journal Article] Regioselective Cycloaddition of La_2@I_h-C_<80> with Tetracyanoethylene Oxide: Formation of an Endohedral Dimetallofullerene Adduct Featuring Enhanced Electron-Accepting Character (2011)
  • Author(s): M. Yamada, M. Minowa, S. Sato, Z. Slanina, T. suchiya, Y. Maeda, S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 3796-3799
  • DOI: DOI:10.1002/ange.201100961
  • Peer Reviewed
• [Journal Article] Semi-metallic Single-component Crystal of Soluble La@C_<82> Derivative with High Electron Mobility (2011)
  • Author(s): S. Seki, Y. Honsho, L. Wang, H. Nikawa, G. Luo, J. Lu, M. Haranaka, T. Tsuchiya, S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 2766-2771
  • DOI: DOI:10.1021/ja110465y
  • Peer Reviewed
• [Journal Article] Sc_2C_2@C_<80> Rather than Sc_2@C_<82>:Templated Formation of Unexpected C_<2v>(5)-C_<80> and Temperature-Dependent Dynamic Motion of Internal Sc_2C_2 Cluster (2011)
  • Author(s): H. Kurihara, X. Lu, Y. Iiduka, N. Mizorogi, Z. Slanina, T. Tsuchiya, T. Akasaka, S. Nagase
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 2382-2385
  • DOI: DOI:10.1021/ja1107723
  • Peer Reviewed
• [Journal Article] Radical Derivatives of Insoluble La@C_74: X-ray Structures, Metal Positions and Isomerization (2011)
  • Author(s): X. Lu, H. Nikawa, T. Kikuchi, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
  • Journal Title: Angew. Chem. Int. Ed Volume: 50 Pages: 6356-6359
  • DOI: DOI:10.1002/anie.201100961
  • Peer Reviewed
• [Journal Article] Covalently Linked Porphyrin-La@C_<82> Hybrids: Structural Elucidation and Investigation of Intramolecular Interactions (2011)
  • Author(s): L. Feng, Z. Slanina, S. Sato, K. Yoza, T. Tsuchiva, N. Mizorogi, T. Akasaka, S. Nagase, N. Martin, D. M. Guldi
  • Journal Title: Angew. Chem. Int. Ed Volume: 50 Pages: 5909-5912
  • DOI: DOI:10.1002/anie.201100432
  • Peer Reviewed
• [Journal Article] Thermal Carbosilylation of Endohedral Dimetallofullerene La_2@I_h-C_<80> with Silirane (2010)
  • Author(s): M. Yamada, M. Minowa, S. Sato, M. Kako, Z. Slanina, N. Mizorogi, T. Tsuchiya, Y. Maeda, S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 132 Pages: 17953-17960
  • DOI: DOI:10.1021/ja108671b
  • Peer Reviewed
• [Journal Article] Photochemical Addition of C_<60> with Siliranes: Synthesis and Characterization of Carbosilylated and Hydrosilylated C_<60> Derivatives (2010)
  • Author(s): J. Nagatsuka, S. Sugitani, M. Kako, T. Nakahodo, N. Mizorogi, M.0. Ishitsuka, Y. Maeda, T. Tsuchiva, T. Akasaka, X. Gao, S. Nagase
  • Journal Title: J. Am. Chem. Soc Volume: 132 Pages: 12106-12120
  • DOI: DOI:10.1021/ja1049719
  • Peer Reviewed
• [Journal Article] A Molecular Ce_2@I_h-C_<80> Switch - Unprecedented Oxidative Pathway in Photoinduced Charge Transfer Reactivity (2010)
  • Author(s): D. M. Guldi, L. Feng, S. G. Radhakrishnan, H. Nikawa, M. Yamada, N. Mizorogi, T. Tsuchiya, T. Akasaka, S. Nagase, M. A. Herranz, N. Martin
  • Journal Title: J. Am. Chem. Soc Volume: 132 Pages: 9078-9086
  • DOI: DOI:10.1021/ja101856j
  • Peer Reviewed
• [Journal Article] Donor-Acceptor Conjugates of Lanthanum Endohedral Metallofullerene and π-Extended Tetrathiafulvalene (2010)
  • Author(s): Y. Takano, M. A. Herranz, N. Martin, S. G. Radhakrishnan, D. M. Guldi, T. Tsuchiya, S. Nagase, T. Akasaka
  • Journal Title: J. Am. Chem. Soc Volume: 132 Pages: 8048-8055
  • DOI: DOI:10.1021/ja100665q
  • Peer Reviewed
• [Journal Article] Yb@C_<2n> (n=40, 41, 42):New Fullerene Allotropes with Unexplored Electrochemical Properties (2010)
  • Author(s): X. Lu, Z. Slanina, T. Akasaka, T. Tsuchiya, N. Mizorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc Volume: 132 Pages: 5896-5905
  • DOI: DOI:10.1021/ja101131e
  • Peer Reviewed
• [Journal Article] Nitrated Benzyne Derivatives of La@C_<82>: Addition of NO_2 and Its Positional Directing Effect on the Subsequent Addition of enzynes (2010)
  • Author(s): X. Lu, H. Nikawa, T. Tsuchiya, T. Akasaka, M. Toki, H. Sawa, N. Mizorogi, S. Nagase
  • Journal Title: Angew. Chem. Int. Ed Volume: 49 Pages: 594-597
  • DOI: DOI:10.1002/anie.200905024
  • Peer Reviewed
• [Journal Article] The Effect of Atomic Nitrogen on the C_<60> Cage (2010)
  • Author(s): H. Nikawa, Y. Araki, Z. Slanina, T. Tsuchiya, T. Akasaka, T. Wada, 0. Ito, K.-P. Dinse, M. Ata, T. Kato, S. Nagase
  • Journal Title: Chem. Commun Volume: 46 Pages: 631-633
  • DOI: DOI:10.1039/b914624e
  • Peer Reviewed
• [Presentation] フラーレンを鍵物質とする高次π空間の創発と機能開拓 (2013)
  • Author(s): 赤阪健
  • Organizer: 科研費新学術領域研究「融合マテリアル」第6回公開シンポジウム
  • Place of Presentation: 仙台市
  • Year and Date: 2013-01-28
• [Presentation] New Vistas in Fullerene Chemistry: Oraganosulfur Compounds Expand the Performance of Carbon Nanomaterials (2012)
  • Author(s): Takeshi Akasaka
  • Organizer: 25th International Symposium on the Organic Chemistry of Sulfur
  • Place of Presentation: Czestochowa, Poland
  • Year and Date: 20120624-29
• [Presentation] フラーレンを鍵物質とする高次π空間の創発と機能開拓 (2012)
  • Author(s): 赤阪健
  • Organizer: 第6回有機π電子系シンポジウム
  • Place of Presentation: 道後温泉茶波瑠、松山市
  • Year and Date: 2012-12-14
• [Presentation] New Vistas in Chemistry of Nanocarbons: Organic Nanomaterials Based on Endohedral Metallofullerenes (2012)
  • Author(s): Takeshi Akasaka
  • Organizer: The Symposium on Material Chemistry in Heilongjiang University
  • Place of Presentation: Harbin, China
  • Year and Date: 2012-09-14
• [Presentation] New Vistas in Chemistry of Nanocarbons: Organic Nanomaterials Based on Endohedral Metallofullerenes (2012)
  • Author(s): 赤阪健
  • Organizer: 岡山大学異分野研究連携コア講演会
  • Place of Presentation: 岡山大学、岡山
  • Year and Date: 2012-08-07
• [Presentation] New Vistas in Chemistry of Synthetic Carbon Allotropes: Organic Nanomaterials Based on Endohedral Metallofullerenes (2012)
  • Author(s): Takeshi Akasaka
  • Organizer: 9th International Conference on Nanosciences & Nanotechnologies
  • Place of Presentation: Thessaloniki, Greece
  • Year and Date: 2012-07-03
• [Presentation] New Vistas in Chemistry of Synthetic Carbon Allotropes: Organic Nanomaterials Based on Endohedral Metallofullerenes (2012)
  • Author(s): Takeshi Akasaka
  • Organizer: 49th Outstanding Scholors Forum in Huazhong University of Science and Technology
  • Place of Presentation: Wuhan, China
  • Year and Date: 2012-06-05
• [Presentation] 金属内包フラーレンを鍵物質とした有機ドナー分子との超分子系の構築 (2011)
  • Author(s): 土屋敬広・青山亮・佐久間理子・溝呂木直美・赤阪健・Dirk M. Guldi・加藤立久・永瀬_茂
  • Organizer: 第38回有機典型元素化学討論会
  • Place of Presentation: 石川県立音楽堂邦楽ホール
  • Year and Date: 2011-12-09
• [Presentation] Electronic Modulation of Endohedral Metallofullerenes by Chemical Functionalization (2011)
  • Author(s): T. Akasaka, M. Yamada, M. Minowa, S. Sato, N. Mizorogi, Z. Slanina, T. Tsuchiya, Y. Maeda, S. Nagase
  • Organizer: 14th International Synlposium on Novel Aromatic Compounds (ISNA-14)
  • Place of Presentation: Oregon, USA
  • Year and Date: 2011-07-24
• [Presentation] 金属内包フラーレンを鍵物質とした超分子系の構築 (2010)
  • Author(s): 土屋敬広・横澤裕也・赤阪健・DirkM.Guldi・永瀬二茂
  • Organizer: 日本化学会第4回関東支部大会
  • Place of Presentation: 筑波大学
  • Year and Date: 2010-08-30
• [Book] Stability Computations for Fullerenes and Metallofullerenes (2012)
  • Author(s): Z. Slanina, F. Uhlik, S-L. Lee, T. Akasaka and S. Nagase
  • Total Pages: Vol.4, 381-429
  • Publisher: In "Handbook of Carbon Nano Materials" F. D'Souza & K. M. Kadish, Eds.; World Scientific
• [Book] Chemistry of Nanocarbons (2010)
  • Author(s): T. Akasaka, F. Wudl, amd .S. Nagase Eds
  • Total Pages: 498
  • Publisher: Wiley-Blackwell, Chichester
• [Remarks]
  • URL: http://www.tara.tsukuba.ac.jp/～akasaka-lab/
• [Patent(Industrial Property Rights)] 有機修飾カーボンナノチューブの製造方法 (2009)
  • Inventor(s): 前田 優・赤阪 健
  • Industrial Property Rights Holder: 独立行政法人科学技術振興機構
  • Industrial Property Number: 特願、2009-060193
  • Filing Date: 2009-03-12