組織化常磁性フラーレンの創製と機能

2011 Fiscal Year Annual Research Report

• Project/Area Number: 20245006
• Research Institution: University of Tsukuba
• Principal Investigator: 赤阪 健 筑波大学, 数理物質系, 教授 (60089810)
• Co-Investigator(Kenkyū-buntansha): 土屋 敬広 筑波大学, 数理物質系, 講師 (10375412) ; 生沼 みどり 筑波大学, 数理物質系, 講師 (20323256)
• Keywords: フラーレン / 科学修飾 / 集積化 / FET

Research Abstract

次世代を切り拓く革新的な電子・光・磁気機能を有する物質の創出を図るため、本研究では磁性内包フラーレンに着目し、その分子変換による構造および電子特性の制御を行う。さらに、得られた常磁性内包フラーレン誘導体の組織化を行い、革新的機能を有する材料の創製を目的とする。
前年度に引き続き常磁性内包フラーレン(La@C82,Ce@C82,Ce2@C8。等)の大量合成と分離精製を行なった。合成した常磁性内包フラーレンについて、選択的光ケイ素化反応、1,3-双極子環化付加反応およびカルベン付加反応を用いた置換基の導入を行い、置換基および付加位置の異なる数種の常磁性内包フラーレン誘導体を合成した。誘導体の構造は単結晶X線結晶構造解析により決定した。
常磁性内包フラーレン誘導体の組織化体ナノロッド(ナノサイズの針状結晶)の作成を行なった。組織化条件を検討することで、様々な形態およびサイズの集合体を作成した。組織化常磁性内包フラーレンの物性評価として、電子移動度の測定による電荷輸送特性を調べた。誘導体La@C82Adの単結晶およびナノロッドでは異方的な伝導度が観測され、また、これまで報告された電子共役系有機材料の中でも格段に高い電子移動度を示した。これは配向制御されたLa@C82誘導体が非常に優れた電荷輸送特性を有することを示す結果である。常磁性金属内包フラーレンを用いた新規有機材料の開拓に期待が持てると言える。

Research Products

• [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
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 13280-13283
  • DOI: 10.1021/ja205391v
  • Peer Reviewed
• [Journal Article] Crystallographic X-ray Analyses of Yb@C_<2v>(3)-C_<80> Reveal a Feasible Rule That Governs the Location of a Rare Earth Metal inside a Medium-Sized Fullerene (2011)
  • Author(s): X.Lu, Y.Lian, C.Beavers, N.Mizorogi, Z.Slanina, S.Nagase, T.Akasaka
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 10772-10775
  • DOI: 10.1021/ja204653z
  • Peer Reviewed
• [Journal Article] Ferromagnetic Spin Coupling between Endohedral Metallofullerene La@C_<82> and a Cyclodimeric Copper Porphyrin upon Inclusion (2011)
  • Author(s): F.Hajjaj, K.Tashiro, H.Nikawa, N.Mizorogi, T.Akasaka, S.Nagase, K.Furukawa, T.Kato, T.Aida
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 9290-9292
  • DOI: 10.1021/ja203491s
  • 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: 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: 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 Enhaneed 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: 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: 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: 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: 10.1002/ange.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: 10.1002/anie.201100432
  • Peer Reviewed
• [Journal Article] Highly Regioselective Synthesis of Bis-Aziridino[60]fullerene with Sulfilimine (2011)
  • Author(s): M.Okada, T.Nakahodo, M.O.Ishitsuka, H.Nikawa, T.Tsuchiya, T.Akasaka, T.Fujie, T.Yoshimura, Z.Slanina, S.Naga
  • Journal Title: Chem.Asian J. Volume: 6 Pages: 416-423
  • DOI: 10.1002/asia.201000244
  • Peer Reviewed
• [Journal Article] Oxygen Atom Transfer from Peroxide Intermediates to Fullerenes (2011)
  • Author(s): Y.Maeda, Y.Niino, T.Kondo, M.Yamada, T.Hasegawa, T.Akasaka
  • Journal Title: Chem.Lett. Volume: 40 Pages: 1431-1433
  • DOI: CL-110702
  • Peer Reviewed
• [Journal Article] Preparation and Characterization of Transparent and Conductive Thin Films of Single-Walled Carbon Nanotubes (2011)
  • Author(s): Y.Maeda, K.Komoriya, K.Sode, J.Higo, T.Nakamura, M.Yamada, T.Hasegawa, T.Akasaka, T.Saito, J.Lu, S.Nagase
  • Journal Title: Nanoscale Volume: 3 Pages: 1904-1909
  • DOI: 10.1039/c0nr00940g
  • Peer Reviewed
• [Journal Article] Synthesis of Endohedral Metallofullerene Glycoconjugates by Carbene Addition (2011)
  • Author(s): M.Yamada, C.I.Someya, T.Nakahodo, Y.Maeda, T.Tsuchiya, T.Akasaka
  • Journal Title: Molecules Volume: 16 Pages: 9495-9504
  • DOI: 10.3390/molecules16119495
  • Peer Reviewed
• [Journal Article] Calculated Relative Yields for Sc_2S@C_<82> and Y_2S@C_<82> (2011)
  • Author(s): Z.Slanina, F.Uhlik, S.-L.Lee, N.Mizorogi, T.Akasaka, L.Adamowicz
  • Journal Title: Theor.Chem.Acc. Volume: 130 Pages: 549-554
  • DOI: 10.3390/molecules16119495
  • Peer Reviewed
• [Journal Article] Introduction of Azetidinimine Skeleton on C_<60> (2011)
  • Author(s): N.Ueda, H.Nikawa, Y.Takano, M.O.Ishitsuka, T.Tsuchiya, T.Akasaka
  • Journal Title: Heteroat.Chem. Volume: 2 Pages: 426-431
  • DOI: 10.1002/hc
  • Peer Reviewed
• [Journal Article] Organosulfur-based Fullerene Materials (2011)
  • Author(s): T.Nakahodo, M.O.Ishitsuka, Y.Takano, T.Tsuchiya, T.Akasaka, A.Herranz, N.Martin, D.M.Guldi, S.Nagase
  • Journal Title: Phosphorus, Sulfur, Silicon Relat.Elem. Volume: 186 Pages: 1308-1311
  • DOI: 10.1080/10426507.2010.523033
• [Journal Article] 金属内包フラーレン:その構造と電子的特性を制御する (2011)
  • Author(s): 山田道夫、佐藤悟、赤阪健、永瀬茂
  • Journal Title: 化学 Volume: 66 Pages: 68-69
• [Journal Article] Current Progress on the Chemical Functionalization and Supramolecular Chemistry of M@C_<82> (2011)
  • Author(s): Y.Maeda, T.Tsuchiya, X.Lu, Y.Takano, T.Akasaka, S.Nagase
  • Journal Title: Nanoscale Volume: 3 Pages: 2421-2429
  • DOI: 10.1039/C0NR00968G
  • Peer Reviewed
• [Journal Article] Chemistry of endohedral metallofullerenes : the role of metals (2011)
  • Author(s): X.Lu, T.Akasaka, S.Nagase
  • Journal Title: Chem.Commun. Volume: 47 Pages: 5942-5957
  • DOI: 10.1039/clcc10123d
  • Peer Reviewed
• [Journal Article] 常磁性金属内包フラーレン誘導体電荷輸送特性 (2011)
  • Author(s): 佐藤悟、関修平、永瀬茂、赤阪健
  • Journal Title: PEN Volume: 1 Pages: 13-13
• [Presentation] 開口部を有する金属内包フラーレン誘導体の合成 (2012)
  • Author(s): 栗原広樹・飯塚裕子・イヴルービン・マーカスヴェルヒリ・溝呂木直美・ズデネクスラニナ・土屋敬広・永瀬茂・赤阪健
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応義塾大学(横浜)
  • Year and Date: 2012-03-25
• [Presentation] 金属内包フラーレンLa_2@C_<80>ラジカル誘導体の合成とキャラクタリゼーション (2012)
  • Author(s): 齋藤正義・栗原広樹・相澤俊博・加藤立久・ズデネクスラニナ・永瀬茂・赤阪健
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応義塾大学(横浜)
  • Year and Date: 2012-03-25
• [Presentation] 金属クラスター内包フラーレン誘導体の合成と構造解析 (2012)
  • Author(s): 阿部玄之・佐藤悟・斎藤千春・SLANINA Z.・土屋敬広・赤阪健・永瀬茂
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応義塾大学(横浜)
  • Year and Date: 2012-03-25
• [Presentation] ラジカル付加反応によるLa_2@C82の可逆的電子状態制御 (2012)
  • Author(s): 高野勇太・生沼みどり・スラニナズデネク・赤阪健・加藤立久・永瀬茂
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応義塾大学(横浜)
  • Year and Date: 2012-03-25
• [Presentation] Structures and Chemical Properties of Carbide Cluster Fullerenes (2012)
  • Author(s): Xing Lu, Hiroki Kurihara, Koji Nakajima, Naomi Mizorogi, Takeshi Akasaka, Shigeru Nagase
  • Organizer: 第42回フラーレン・ナノチューブ・グラフェン総合シンポジウム
  • Place of Presentation: 東京大学(東京)
  • Year and Date: 2012-03-06
• [Presentation] New Vistas in Chemistry of Nanocarbons : Organic Nanomaterials Based on Endohedral Metallofullerenes (2012)
  • Author(s): Takeshi Akasaka
  • Organizer: Forum for Nano-Materials Science 2012
  • Place of Presentation: Xi'an Jiaotong University, Xi'an, China(招待講演)
  • Year and Date: 2012-01-14
• [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・DirkM.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(金沢)
  • Year and Date: 2011-12-07
• [Presentation] 化学修飾によるLa_2@C_<80>の電子アクセプター性制御 (2011)
  • Author(s): 山田道夫・美野輪まり・佐藤悟・溝呂木直美・Zdenek Slanina・前田優・加固昌寛・永瀬茂・赤阪健
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: つくば国際会議場(つくば)
  • Year and Date: 2011-09-21
• [Presentation] 金属内包フラーレンSc_2C_<82>の構造決定とキャラクタリゼーション (2011)
  • Author(s): 栗原広樹・山崎裕子・溝呂木直美・Zdenek Slanina・土屋敬広・赤阪健・永瀬茂
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: つくば国際会議場(つくば)
  • Year and Date: 2011-09-21
• [Presentation] 常磁性金属内包フラーレン多付加体の合成 (2011)
  • Author(s): 阿部玄之・佐藤悟・田邊由紀子・溝呂木直美・前田優・土屋敬広・赤阪健・永瀬茂
  • Organizer: 日本化学会第5回関東支部大会(2011)
  • Place of Presentation: 東京農工大(東京)
  • Year and Date: 2011-08-30
• [Presentation] La内包フラーレン/有機ドナー連結系の構築 (2011)
  • Author(s): 中田輝・土屋敬広・赤阪健・永瀬茂
  • Organizer: 日本化学会第5回関東支部大会(2011)
  • Place of Presentation: 東京農工大(東京)
  • Year and Date: 2011-08-30
• [Presentation] 金属内包フラーレンの骨格変換 (2011)
  • Author(s): 武藤康弘・栗原広樹・Zdenek Slanina・土屋敬広・赤阪健・永瀬茂
  • Organizer: 日本化学会第5回関東支部大会(2011)
  • Place of Presentation: 東京農工大(東京)
  • Year and Date: 2011-08-30
• [Presentation] 金属内包フラーレンGd@C_<2v>-C_<82>のX線構造解析 (2011)
  • Author(s): 鈴木光明・佐藤悟・Lu Xing・二川秀史・土屋敬広・溝呂木直美・Zdenek Slanina・赤阪健・永瀬茂
  • Organizer: 日本化学会第5回関東支部大会(2011)
  • Place of Presentation: 東京農工大(東京)
  • Year and Date: 2011-08-30
• [Presentation] New Vistas in Chemistry of Fullerenes : Organic Nanomaterials based on Endohedral Metallofullerenes (2011)
  • Author(s): Takeshi Akasaka
  • Organizer: 43rd IUPAC World Chemistry Congress
  • Place of Presentation: San Juan, Puerto Rico(招待講演)
  • Year and Date: 2011-07-30
• [Presentation] Electronic Modulation of Endohedral Metal lofullerenes by Chemical Functionalization (2011)
  • Author(s): Takeshi Akasaka, Mihico Yamada, Mari Minowa, Satoru Sato, Naomi Mizorogi, Zdenek Slanina, Takahiro Tsuchiya, Yutaka Maeda, Shigeru Nagase
  • Organizer: 14th International Symposium on Novel Aromatic Compounds (ISNA-14)
  • Place of Presentation: Oregon, USA
  • Year and Date: 2011-07-24
• [Presentation] New Vistas in Chemistry of Synthetic Carbon Allotopes : Organic Nanomaterials based on Endohedral Metallofullerenes (2011)
  • Author(s): Takeshi Akasaka
  • Organizer: The First Symposium on "Carbon Nanoforms" at Nanoscience, Nanotechnology and Molecular Materials Institute (INAMOL-UCLM)
  • Place of Presentation: Toledo, Spain(招待講演)
  • Year and Date: 2011-06-02
• [Presentation] Tuning of electronic properties of endohedral dimetallofullerene La_2@C_<80> by exohedral chemical functionalization (2011)
  • Author(s): Michio Yamada, Mari Minowa, Satoru Sato, Naomi Mizorogi, Zdenek Slanina, Takahiro Tsuchiya, Yutaka Maeda, Shigeru Nagase, Takeshi Akasaka
  • Organizer: The First Symposium on "Carbon Nanoforms" at Nanoscience, Nanotechnology and Molecular Materials Institute (INAMOL-UCLM)
  • Place of Presentation: Toledo, Spain
  • Year and Date: 2011-06-02
• [Presentation] Synthesis and Characterization of the Conjugates Based on La_2@C_<80> and pi-Extended Tetrathiafulvalene (2011)
  • Author(s): Yuta Takano, Lai Feng, Maria Angeles Herranz, Nazario Martin, Shankara Gayathri Radhakrishnan, Dirk M.Guldi, Takeshi Akasaka
  • Organizer: The First Symposium on "Carbon Nanoforms" at Nanoscience, Nanotechnology and Molecular Materials Institute (INAMOL-UCLM)
  • Place of Presentation: Toledo, Spain
  • Year and Date: 2011-06-02
• [Presentation] The Role that Internal Metals Play in Endohedral Metallofullerenes (2011)
  • Author(s): Xing Lu, Hidefumi Nikawa, Naomi Mizorogi, Zdenek Slanina, Takeshi Akasaka, Shigeru Nagase
  • Organizer: 219th ECS Meeting
  • Place of Presentation: Montreal, Canada
  • Year and Date: 2011-05-01
• [Book] カーボンナノチューブへのカルボキシル基導入とその官能基変換 (2011)
  • Author(s): 前田優、赤阪健、山田道夫、長谷川正
  • Total Pages: 61-71(11)
  • Publisher: 技術情報協会出版
• [Book] アミンによる単層カーボンナノチューブの分散と分離 (2011)
  • Author(s): 前田優、赤阪健、山田道夫、長谷川正
  • Total Pages: 51-60(10)
  • Publisher: 技術情報協会出版
• [Remarks]
  • URL: http://www.tara.tsukuba.ac.jp/~akasaka-lab/
• [Remarks]
  • URL: http://www.pi-space.jp/