Construction and properties of aggregated paramagnetic fullerenes

2011 Fiscal Year Final Research Report

• Project/Area Number: 20245006
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• 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) ; OINUMA Midori 筑波大学, 数理物質系, 講師 (20323256)
• Co-Investigator(Renkei-kenkyūsha): NAGASE Shigeru 分子科学研究所, 理論分子科学研究系, 教授 (30134901) ; MAEDA Yutaka 東京学芸大学, 教育学部, 准教授 (10345324) ; YAMADA Michio 東京学芸大学, 教育学部, 助教 (00583098)
• Project Period (FY): 2008 – 2011
• 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 metallofullerenes remains 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] 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. Akasaka
  • 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
  • Peer Reviewed
• [Journal Article] X-Ray Structures of Sc_2C_2@C_<2n> (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. Nagase, T. Akasaka
  • Journal Title: Inorg. Chem. Volume: 51 Pages: 746-750
  • 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. Commun. 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. Tsuchiya, 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. Tsuchiya, M. Wielopolski, N. Sakuma, N. Mizorogi, T. Akasaka, T. Kato, D. M. Guldi
  • Journal Title: S. NagaseJ. Am. Chem. Soc. Volume: 133 Pages: 13280-13283
  • Peer Reviewed
• [Journal Article] Synthesis and Charge-Transfer Chemistry of La_2@Ih-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
  • Journal Title: D. GuldiJ. 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. Tsuchiya, 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. Sato, 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
  • Journal Title: S. NagaseJ. 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. Tsuchiya, 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@Ih-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. O. Ishitsuka, Y. Maeda, T. Tsuchiya, T. Akasaka, X. Gao
  • Journal Title: S. Nagase J. Am. Chem. Soc. Volume: 132 Pages: 12106-12120
  • DOI: DOI:10.1021/ja1049719
  • Peer Reviewed
• [Journal Article] A Molecular Ce_2@Ih-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, A N. Mizorogi
  • Journal Title: S. NagaseJ. Am. Chem. Soc. Volume: 132 Pages: 5896-5905
  • DOI: DOI:10.1021/ja101131e
  • Peer Reviewed
• [Journal Article] Nitrated Benzyne Derivatives ofLa@C_<82> : Addition of NO_2 and Its Positional Directing Effect on the Subsequent Addition of Benzynes (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 theC_<60> Cage (2010)
  • Author(s): H. Nikawa, Y. Araki, Z. Slanina, T. Tsuchiya, T. Akasaka, T. Wada, O. Ito, K.-P. Dinse, M. Ata, T. Kato
  • Journal Title: S. NagaseChem. Commun. Volume: 46 Pages: 631-633
  • DOI: DOI:10.1039/b914624e
  • Peer Reviewed
• [Presentation] 「組織化常磁性内包フラーレンの分子変換と電子移動挙動」(依頼講演) (2012)
  • Author(s): 土屋敬広, 赤阪健, 関修平, 谷垣勝己
  • Organizer: 第59回応用物理学関係連合講演会
  • Place of Presentation: 早稲田大学
  • Year and Date: 2012-03-17
• [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 Symposium on Novel Aromatic Compounds (ISNA-14)
  • Place of Presentation: Oregon, USA
  • Year and Date: 2011-07-24
• [Presentation] 組織化常磁性内包フラーレンの創製 (2011)
  • Author(s): 土屋敬広, 赤阪健, 関修平, 谷垣勝己
  • Organizer: 第58回応用物理学関係連合講演会
  • Place of Presentation: 神奈川工科大学
  • Year and Date: 2011-03-25
• [Presentation] 「金属内包フラーレンに基づく超分子系の構築」(依頼講演) (2011)
  • Author(s): 土屋敬広, 赤阪健
  • Organizer: 筑波大学戦略イニシアティブ(A)「機能物質創製研究拠点」第1回若手シンポジウム
  • Place of Presentation: 筑波大学
  • Year and Date: 2011-01-05
• [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, Dirk M. Guldi, 永瀬茂
  • 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] Chemistry of Nanocarbons (2010)
  • Author(s): F. Wudl, amd S. Nagase Eds.
  • Total Pages: 498
  • Publisher: Wiley-Blackwell, Chichester
• [Remarks]
  • URL: http://www.tara.tsukuba.ac.jp/~akasakalab/
• [Patent(Industrial Property Rights)] 窒素内包フラーレン類の分離精製法 (2010)
  • Inventor(s): 赤阪健
  • Industrial Property Rights Holder: 国立大学法人筑波大学
  • Industrial Property Number: 特許、第4528906号
  • Acquisition Date: 2010-06-18
• [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: 特許、第4528906号
  • Filing Date: 2009-03-12