Construction and properties of supramolecular system based on paramagnetic endofullerenes

2011 Fiscal Year Final Research Report

• Project/Area Number: 22750030
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: University of Tsukuba
• Principal Investigator: TSUCHIYA Takahiro 筑波大学, 数理物質系, 講師 (10375412)
• Project Period (FY): 2010 – 2011
• Keywords: 内包フラーレン / 自己組織化 / 合成化学 / スピンエレクトロニクス

Research Abstract

Paramagnetic endohedral metallofullerene ligand, which has a pyridine moiety as a ligation moiety for metal complexes, was synthesized selectively by the [2 + 3] cycloaddition reaction of La@C82 with azomethine ylide. Supramolecular complexes of the metallofullerene ligands with metalloporphyrin and fused metalloporphyrin dimer were constructed.

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
  • DOI: DOI:10.1002/anie.201106912
  • 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
  • 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. 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, S. Nagase J
  • Journal Title: 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. 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, 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. 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@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. O. Ishitsuka, Y. Maeda, T. Tsuchiya, 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: 078-9086
  • 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 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 the C_<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 (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] フラーレン科学の新展開:金属内包フラーレンの化学 (2012)
  • Author(s): 土屋敬広
  • Organizer: 群馬大学工学系フロンティアリーダーコース先端研究紹介講座
  • Place of Presentation: 群馬大学
  • Year and Date: 2012-01-16
• [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] ナノカーボンの新展開:金属内包フラーレンの化学 (2011)
  • Author(s): 土屋敬広
  • Organizer: CSJ化学フェスタ新化学技術推進協会奨励研究講演会.将来の化学産業を切り拓く先進技術.
  • Place of Presentation: 早稲田大学
  • Year and Date: 2011-11-14
• [Presentation] Construction of Supramolecular System Based on Endohedral Metallofullerene (2011)
  • Author(s): T. Tsuchiya
  • Organizer: MDF International Workshop : Open-shell Organic Molecules-Synthesis and Electronic Structure Freedom., Umeda Sky Building
  • Place of Presentation: Japan
  • Year and Date: 2011-10-07
• [Presentation] 湾曲型π共役化合物に基づく超分子系の構築 (2011)
  • Author(s): 土屋敬広
  • Organizer: 高次π空間の創発と機能開発第3回若手研究会
  • Place of Presentation: 岡崎コンファレンスセンター
  • Year and Date: 2011-07-16
• [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 (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] Construction of Supramolecular System Based on Endohedral Metallofullerene (2010)
  • Author(s): T. Tsuchiya
  • Organizer: Fullerene Silver Anniversary Symposium 2010
  • Place of Presentation: Crete, Greece
  • Year and Date: 2010-10-07
• [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] Wiley-Blackwell, Chichester (2010)
  • Author(s): T. Tsuchiya, T. Akasaka, S. Nagase inChemistry of Nanocarbons, T. Akasaka,F. Wudl, amd S. Nagase Eds
  • Total Pages: 498
  • Publisher: Recent Progress in Chemistry ofEndohedral Metallofullerenes
• [Remarks]
  • URL: http://www.tara.tsukuba.ac.jp/~akasakalab/