Chemical functionalization and self assembly of paramagnetic carbon clusters

• Project/Area Number: 18685005
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: National Institute for Materials Science (2007-2008); University of Tsukuba (2006)
• Principal Investigator: WAKAHARA Takatsugu National Institute for Materials Science, ナノ物質ラボ, 主幹研究員 (40303177)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥29,770,000 (Direct Cost: ¥22,900,000、Indirect Cost: ¥6,870,000); Fiscal Year 2008: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2007: ¥18,070,000 (Direct Cost: ¥13,900,000、Indirect Cost: ¥4,170,000); Fiscal Year 2006: ¥8,320,000 (Direct Cost: ¥6,400,000、Indirect Cost: ¥1,920,000)
• Keywords: 構造有機化学 / 常磁性 / 炭素クラスター / 金属 / フラーレン

Research Abstract

磁性炭素クラスターの自己集積化によるナノ集合体の創製を行った。合成したナノ集合体を用いて、伝導度測定や磁場配向等を検討し、磁性炭素クラスターのナノ材料としての有用性を確立した。これらの磁性炭素クラスターはその球状構造と高い対称性により、そのままでは磁性炭素クラスターを自在に配列させることは非常に困難である。そこで、本研究では、球状の磁性炭素クラスターを化学修飾することで機能化し、自己集合によるナノ集合体の合成を検討した。

Research Products

• [Journal Article] Location of Metal Atoms Below the Addendum in 6,6-Open Adducts, M2@C80(Ad) (M=La and Ce, Ad=adamantylidene) (2008)
  • Author(s): M. Yamada, C. Someya, T. Wakahara, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, E. Horn, N. Mizorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 1171-1176
  • Peer Reviewed
• [Journal Article] Does Gd@C82 Have an Anomalous Endohedral Structure? Synthesis and Single Crystal X-ray Structure of the Carbene Adduct (2008)
  • Author(s): T. Akasaka, T. Kono, Y. Takematsu, H. Nikawa, T. Nakahodo, T. Wakahara, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, M. T. H. Liu, K. Yoza, T. Kato, K. Yamamoto, N. Mizorogi, Z. Slanina, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 12840-12841
  • Peer Reviewed
• [Journal Article] Radical Coupling Reaction of Paramagnetic Endohedral Metallofullerene La@C82 (2008)
  • Author(s): Y. Takano, A. Yomogida, H. Nikawa, M. Yamada, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, T. Kato, Z. Slanina, N. Mizorogi and S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 16224-16230
  • NAID: 130004645465
  • Peer Reviewed
• [Journal Article] Nanorods of Endohedral Metallofullerene Derivative (2008)
  • Author(s): T. Tsuchiya, R. Kumashiro, K. Tanigaki, Y. Matsunaga, M. O. Ishitsuka, T. Wakahara, Y. Maeda, Y. Takano, M. Aoyagi, T. Akasaka, M. T. H. Liu, T. Kato, K. Suenaga, J. S. Jeong, S. Iijima, F. Kimura, T. Kimura, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 450-451
  • Peer Reviewed
• [Journal Article] Observation of 13C NMR Chemical Shifts of Metal Carbides Encapsulated in Fullerenes : Sc2C2@C82, Sc2C2@C84, and Sc3C2@C80 (2008)
  • Author(s): Y. Yamazaki, K. Nakajima, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, M. Waelchli, N. Mizorogi, S. Nagase
  • Journal Title: Angew. Chem., Int. Ed. Engl 47 Pages: 7905-7908
  • Peer Reviewed
• [Journal Article] Spectroscopic and Theoretical Study of Endohedral Dimetallofullerene Having a Non-IPR Fullerene Cage : Ce2@C72 (2008)
  • Author(s): M. Yamada, T. Wakahara, T. Tsuchiya, Y. Maeda, T. Akasaka, N. Mizorogi, S. Nagase
  • Journal Title: J. Phys. Chem 112 Pages: 7627-7631
  • Peer Reviewed
• [Journal Article] Isolation and Characterization of Carbene Derivatives of La@C82(Cs) (2008)
  • Author(s): T. Akasaka, T. Kono, Y. Matsunaga, T. Wakahara, T. Nakahodo, M. O. Ishitsuka, Y. Maeda, T. Tsuchiya, T. Kato, M. T. H. Liu, N. Mizorogi, Z. Slanina, S. Nagase
  • Journal Title: J. Phys. Chem 112 Pages: 1294-1297
  • Peer Reviewed
• [Journal Article] Location of the metal atoms in Ce2@C78 and its bis-silylated derivative (2008)
  • Author(s): M. Yamada, T. Wakahara, T. Tsuchiya, Y. Maeda, M. Kako, T. Akasaka, K. Yoza, E. Horn, N. Mizorogi, S. Nagase
  • Journal Title: Chem. Commun. Pages: 558-560
  • Peer Reviewed
• [Journal Article] Location of Metal Atoms Below the Addendum in 6,6-Open Adducts, M2@C80(Ad)(M=La and Ce, Ad=adamantylidene) (2008)
  • Author(s): M. Yamada, C. Someya, T. Wakahara, 他
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 1171-1176
  • Peer Reviewed
• [Journal Article] Does Gd@C82 Have an Anomalous Endohedral Structure? Synthesis and Single Crystal X-ray Structure of the Carbene Adduct (2008)
  • Author(s): T. Akasaka, T. Kono, Y. Takematsu, H. Nikawa, T. Nakahodo, T. Wakahara, 他
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 12840-12841
  • Peer Reviewed
• [Journal Article] Radical Coupling Reaction of Paramagnetic Endohedral Metallbfullerene La@C82 (2008)
  • Author(s): Y. Takano, A. Yomogida, H. Nikawa, M. Yamada, T. Wakahara, 他
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 16224-16230
  • Peer Reviewed
• [Journal Article] Nanorods of Endohedral Metallofullerene Derivative (2008)
  • Author(s): T. Tsuchiya, R. Kumashiro, K. Tanigaki, Y. Matsunaga, M. O. Ishitsuka, T. Wakahara, 他
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 450-451
  • Peer Reviewed
• [Journal Article] Observation of 13C NMR Chemical Shifts of Metal Carbides Encapsulated in Fullerenes: Sc2C2@C82, Sc2C2@C84, and SC3C2@C80 (2008)
  • Author(s): Y. Yamazaki, K. Nakajima, T. Wakahara, 他
  • Journal Title: Angew. Chem., Int. Ed. Engl. 47 Pages: 7905-7908
  • Peer Reviewed
• [Journal Article] Spectroscopic and Theoretical Study of Endohedral Dimetallofutierene Having a Non-BPR Fullerene Cage: Ce2@C72 (2008)
  • Author(s): M. Yamada, T. Wakahara, 他
  • Journal Title: J. Phys. Chem. A 112 Pages: 7627-7631
  • Peer Reviewed
• [Journal Article] Isolation and Characterization of Carbene Derivatives of La@C82(Cs) (2008)
  • Author(s): T. Akasaka, T. Kono, Y. Matsunaga, T. Wakahara, 他
  • Journal Title: J. Phys. Chem. A 112 Pages: 1294-1297
  • Peer Reviewed
• [Journal Article] Location of the metal atoms in Ce2@C78 and its bis-silylated derivative (2008)
  • Author(s): M. Yamada, T. Wakahara, 他
  • Journal Title: Chem. Commun. Pages: 558-560
  • Peer Reviewed
• [Journal Article] Two-dimensional hopping motion of encapsulated La atoms in silylated La2@C80 (2007)
  • Author(s): T. Wakahara, M. Yamada, S. Takahashi, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, M. Kako, K. Yoza, E. Horn, N. Mizorogi, and S. Nagase
  • Journal Title: Chem. Commun. Pages: 2680-2682
  • Peer Reviewed
• [Journal Article] Experimental and Theoretical Studies of the Scandium Carbide Endohedral Metallofullerene Sc2C2@C82 and Its Carbene Derivative (2007)
  • Author(s): Y. Iiduka, T. Wakahara, K. Nakajima, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, M. T. H. Liu, N. Mizorogi, and S. Nagase
  • Journal Title: Angew. Chem., Int. Ed. Engl 46 Pages: 5562-5564
  • Peer Reviewed
• [Journal Article] Two-dimensional hopping motion of encapsulated La atoms in silylated La_2 @ C_<80> (2007)
  • Author(s): T. Wakahara他
  • Journal Title: Chem. Commun. Pages: 2680-2682
  • Peer Reviewed
• [Journal Article] Experimental and Theoretical Studies of the Scandium Carbide Endohedral Metallofullerene Sc_2C_2@C_<82> and Its Carbene Derivative (2007)
  • Author(s): Y. Iiduka, T. Wakahara他
  • Journal Title: Angew. Chem., Int. Ed. Engl 46 Pages: 5562-5564
  • Peer Reviewed
• [Journal Article] Photo-labeling of C_<60> with 3-trifluoromethyl-3-phenyldiazirine (2007)
  • Author(s): S. Sato, M. Yamada, T. Wakahara他
  • Journal Title: Tetrahedron Lett. 48, Pages: 6290-6293
  • Peer Reviewed
• [Journal Article] Determination of the photolytic decomposition pathways of benzylchlorodiazirine by C_<60> probe technique (2007)
  • Author(s): M.O. Ishitsuka, H. Enoki, H. Nikawa, T. Wakahara他
  • Journal Title: Tetrahedron Lett., 48 Pages: 859-861
  • Peer Reviewed
• [Journal Article] Extraction of Metallic Nanotubes of Zeolite-Supported Single-Walled Carbon Nanotubes Synthesized from Alcohol (2007)
  • Author(s): Y. Maeda, M. Hashimoto, T. Hasegawa, M. Kanda, T. Tsuchiya, T. Wakahara他
  • Journal Title: NANO 2, Pages: 221-226
  • Peer Reviewed
• [Journal Article] La@C72 Having a Non-IPR Carbon Cage (2006)
  • Author(s): T. Wakahara, H. Nikawa, T. Kikuchi, T. Nakahodo, G.M. Aminur Rahman, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, E. Horn, K. Yamamoto, N. Mizorogi, Z. Slanina, S. Nagase
  • Journal Title: J. Am. Chem. Soc 128 Pages: 14228-14229
  • Peer Reviewed
• [Journal Article] Characterization of the Bis-silylated Endofullerene, Sc3N@C80 (2006)
  • Author(s): T. Wakahara, Y. Iiduka, O. Ikenaga, T. Nakahodo, A. Sakuraba, T. Tsuchiya, Y. Maeda, M. Kako, T. Akasaka, K. Yoza, E. Horn, N. Mizorogi and S. Nagase
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 9919-9925
  • Peer Reviewed
• [Journal Article] Analysis of Lanthanide-Induced NMR Shifts of the Ce@C82 Anion (2006)
  • Author(s): M. Yamada, T. Wakahara, Y. Lian, T. Tsuchiya, T. Akasaka, M. Waelchli, N. Mizorogi, S. Nagase, and K. M. Kadish
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 1400-1401
  • Peer Reviewed
• [Journal Article] Synthesis and Structural Characterization of Endohedral Pyrrolidinodimetallofullerene : La2@C80(CH2)2NTrt (2006)
  • Author(s): M. Yamada, T. Wakahara, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, E. Horn, N. Mizorogi, and S. Nagase
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 1402-1403
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of a Bisadduct of La@C82 (2006)
  • Author(s): L. Feng, T. Tsuchiya, T. Wakahara, T. Nakahodo, Q. Piao, Y. Maeda, T. Akasaka, T. Kato, K. Yoza, E. Horn, N. Mizorogi, and S. Nagase
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 5990-5991
  • Peer Reviewed
• [Journal Article] Spin-Site Exchange System Constructed from Endohedral Metallofullerenes and Organic Donors (2006)
  • Author(s): T. Tsuchiya, K. Sato, H. Kurihara, T. Wakahara, Y. Maeda, T. Akasaka, K. Ohkubo, S. Fukuzumi, T. Kato, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 14418-14419
  • Peer Reviewed
• [Journal Article] Host-Guest Complexation of Endohedral Metallofullerene with Azacrown Ether and Its Application (2006)
  • Author(s): T. Tsuchiya, K. Sato, H. Kurihara, T. Wakahara, T. Nakahodo, Y. Maeda, T. Akasaka, K. Ohkubo, S. Fukuzumi, T. Kato, N. Mizorogi, K. Kobayashi, and S. Nagase
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 6699-6703
  • Peer Reviewed
• [Journal Article] 13C NMR spectroscopic study of scandium dimetallofullerene, Sc2@C84 vs. Sc2C2@C82 (2006)
  • Author(s): Y. Iiduka, T. Wakahara, K. Nakajima, T. Tsuchiya, T. Nakahodo, Y. Maeda, T. Akasaka, N. Mizorogi, and S. Nagase
  • Journal Title: Chem. Commun. Pages: 2057-2059
  • Peer Reviewed
• [Journal Article] The Bingel Monoadducts of La@C82 : Synthesis, Characterization, and Electrochemistry (2006)
  • Author(s): L. Feng, T. Wakahara, T. Nakahodo, T. Tsuchiya, Q. Piao, Y. Maeda, Y. Lian, T. Akasaka, E. Horn, K. Yoza, T. Kato, N. Mizorogi, and S. Nagase
  • Journal Title: Chem. Eur. J. 12 Pages: 5578-5586
  • Peer Reviewed
• [Journal Article] NMR Study of La@C82(Ad) Anion (2006)
  • Author(s): Y. Matsunaga, Y. Maeda, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, T. Akasaka, N. Mizorogi, K. Kobayashi, S. Nagase, and K. M. Kadish
  • Journal Title: ITE Lett 7
  • Peer Reviewed
• [Journal Article] Selective Extraction and Purification of Endohedral Metallofullerene from Carbon Soot (2006)
  • Author(s): T. Tsuchiya, T. Wakahara, Y. Lian, Y. Maeda, T. Akasaka, T. Kato, N. Mizorogi, S. Nagase
  • Journal Title: J. Phys. Chem 110 Pages: 22517-22520
  • Peer Reviewed
• [Journal Article] Supramolecular complexes of La@C82 with unsaturated thiacrown ethers (2006)
  • Author(s): T. Tsuchiya, H. Kurihara, K. Sato, T. Wakahara, T. Akasaka, T. Shimizu, N. Kamigata, N. Mizorogi, S. Nagase
  • Journal Title: Chem. Commun Pages: 3585-3587
  • Peer Reviewed
• [Journal Article] Structure Determination of a Missing-caged Metallofullerene: Yb@C74 (II) and the Dynamic Motion of the Encaged Ytterbium Ion (2006)
  • Author(s): J. Xu, T. Tsuchiya, C. Hao, Z. Shi, T. Wakahara, W. Mi, Z. Gu and T. Akasaka
  • Journal Title: Chem. Phys. Lett 419 Pages: 44-47
  • Peer Reviewed
• [Journal Article] The Stability of Singly and Multiply Charged La2@C80 and La@C82 Ions Determined from Kinetic Energy Release Measurements (2006)
  • Author(s): S. Feil, K. Gluch, S. Matt-Leubner, O. Echt, C. Lifshitz, B. Cao, T. Wakahara, T. Akasaka, P. Scheier and T. D. Maerk
  • Journal Title: Int. J. Mass Spec 249/250 Pages: 396-402
  • Peer Reviewed
• [Journal Article] La@C_<72> Having a Non-IPR Carbon Cage (2006)
  • Author(s): T.Wakahara他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 14228-14228
• [Journal Article] Characterization of the Bis-silylated Endofullerene, Sc_3N@ C_<80> (2006)
  • Author(s): T.Wakahara他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 9919-9919
• [Journal Article] Analysis of Lanthanide-Induced NMR Shifts of the Ce@C_<82> Anion (2006)
  • Author(s): M.Yamada他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 1400-1400
• [Journal Article] Synthesis and Structural Characterization of Endohedral Pyrrolidinodimetallofullerene : La_2@C_<80>(CH_2)_2NTrt (2006)
  • Author(s): M.Yamada他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 1402-1402
• [Journal Article] Synthesis and Characterization of a Bisadduct of La@C_<82> (2006)
  • Author(s): L.Feng他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 5590-5590
• [Journal Article] Spin-Site Exchange System Constructed from Endohedral Metallofullerenes and Organic Donors (2006)
  • Author(s): T.Tsuchiya他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 14418-14418
• [Journal Article] Selective Extraction and Purification of Endohedral Metallofullerene from Carbon Soot (2006)
  • Author(s): T.Tsuchiya他
  • Journal Title: J.Phys.Chem.B 110 Pages: 22517-22517
• [Journal Article] The Bingel Monoadducts of La@C_<82> : Synthesis, Characterization, and Electrochemistry (2006)
  • Author(s): L.Feng他
  • Journal Title: Chem.Eur.J. 12 Pages: 5578-5578
• [Journal Article] Supramolecular Complexes of La@C_<82> with Unsaturated Thiacrown Ethers (2006)
  • Author(s): T.Tsuchiya他
  • Journal Title: Chem.Commun. Pages: 3585-3585
• [Journal Article] Preparation of Single-Walled Carbon Nanotube-Organosilicon Hybrids and Their Enhanced Field Emission Properties (2006)
  • Author(s): Y.Maeda他
  • Journal Title: Chem.Mater. 18 Pages: 4205-4205
• [Journal Article] Dispersion and Separation of Small Diameter Single-Walled Carbon Nanotubes (2006)
  • Author(s): Y.Maeda他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 12239-12239
• [Journal Article] Host-Guest Complexation of Endohedral Metallofullerene with Azacrown Ether and Its Application (2006)
  • Author(s): T.Tsuchiya他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 6699-6699
• [Journal Article] ^<13>C NMR Spectroscopic Study of Scandium Dimetallofullerene, Sc_2@C_<84> vs. Sc_2C_2@C_<82> (2006)
  • Author(s): Y.Iiduka他
  • Journal Title: Chem.Commun. Pages: 2057-2057
• [Journal Article] NMR study of La@C_<82>(Ad) anion (2006)
  • Author(s): Y.Matsunaga他
  • Journal Title: ITE Lett. 7 Pages: 43-43
• [Journal Article] Selective Interaction o Large or Charge-Transfer Aromatic Molecules with Metallic Single-Wall Carbon Nanotubes : Critical Role of the Molecular Size and Orientation (2006)
  • Author(s): J.Lu他
  • Journal Title: J.Am.Chem.Soc. 128 Pages: 5114-5114
• [Journal Article] Evolution of the Electronic Properties of Metallic Single-Walled Carbon Nanotubes with the Degree of CCl_2 Covalent Functionalization (2006)
  • Author(s): J.Lu他
  • Journal Title: J.Phys.Chem.B 110 Pages: 5655-5655
• [Journal Article] Structure Determination of a Missing-caged Metallofullerene : Yb@C_<74>(II) and the Dynamic Motion of the Encaged Ytterbium Ion (2006)
  • Author(s): J.Xu他
  • Journal Title: Chem.Phys.Lett. 419 Pages: 44-44
• [Journal Article] Preparation and Electrochemical Properties of 1,4,8,11,15,18,22,25-Octalkylphthalocyanines Containing Four Trithiole Rings (2006)
  • Author(s): T.Kimura他
  • Journal Title: Eur.J.Org.Chem. 5 Pages: 1262-1262
• [Journal Article] The Stability of Singly and Multiply Charged La@C_<80> and La@C_<82> Ions Determined from Kinetic Energy Release Measurements (2006)
  • Author(s): S.Feil他
  • Journal Title: Int.J.Mass Spec. 249/250 Pages: 396-396
• [Presentation] Fullerene-based supramolecular nanoarchitectures (2008)
  • Author(s): 若原孝次
  • Organizer: Germany-Japan Workshop
  • Place of Presentation: 東京
  • Year and Date: 2008-02-14
• [Presentation] Metal/Carbon Hybrid Nanoarchitectures (2008)
  • Author(s): T. Wakahara et al
  • Organizer: IUMRS 2008
  • Place of Presentation: 名古屋
• [Presentation] フラーレンナノウイスカーの直径制御と電子状態 (2008)
  • Author(s): 若原孝次 他
  • Organizer: 第17回有機結晶シンポジウム
  • Place of Presentation: 大阪
• [Presentation] フラーレンナノウイスカーの直径制御と電子状態 (2008)
  • Author(s): 若原孝次, 他
  • Organizer: 第17回有機癌晶シンポ
  • Place of Presentation: 大阪大学
• [Presentation] Metal/Carbon Hybrid Nanoarcbitectures (2008)
  • Author(s): 若原孝次, 他
  • Organizer: IUMRS-ICA 2008
  • Place of Presentation: 名古屋国際会議場
• [Presentation] 金属内包フラーレンの化学修飾 (2007)
  • Author(s): 若原孝次 他
  • Organizer: 第68回応用物理学会
  • Place of Presentation: 札幌
  • Year and Date: 2007-09-04
• [Presentation] 金属内包フラーレンの化学修飾 (2007)
  • Author(s): 若原孝次, 他
  • Organizer: 第68回 応用物理学会
  • Place of Presentation: 札幌
  • Year and Date: 2007-09-04
• [Presentation] Organic Metal Doped Fullerene Nanowhiskers (2007)
  • Author(s): T. Wakahara et. Al
  • Organizer: ISNEPP 2007
  • Place of Presentation: フロリダ
• [Presentation] Organic Metal Doped Fullerene Nanowhiskers (2007)
  • Author(s): 若原孝次, 他
  • Organizer: ISNEPP 2007
  • Place of Presentation: アメリカ