Organic Synthesis of Novel Endohedral Fullerenes by the Method of Molecular Surgery

2008 Fiscal Year Final Research Report

• Project/Area Number: 19020067
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Fukui University of Technology
• Principal Investigator: KOMATSU Koichi Fukui University of Technology, 工学部, 教授 (70026243)
• Co-Investigator(Kenkyū-buntansha): MURATA Yasujiro 京都大学, 化学研究所, 教授 (40314273) ; MURATA Michihisa 京都大学, 化学研究所, 助教 (30447932)
• Project Period (FY): 2007 – 2008
• Keywords: 合成有機化学

Research Abstract

炭素原子のみからなる球状の分子であるフラーレンの内部空間に小原子や分子を入れた「内包フラーレン」を、従来用いられてきた効率の低い物理的手段ではなく、「分子手術法」とよぶ有機化学的手法によって合成した。すなわち、フラーレン分子C60およびC70について、有機化学反応によってまず骨格に開口部を設け、それを適当なサイズに拡大した後に、ヘリウム、水素、重水素などを内部に入れ、最後に開口部を閉じることによって、これらの化学種を含んだ内包フラーレンを合成することに初めて成功した。

Research Products

• [Journal Article] Synthesis and Reaction of Fullerene C70 Encapsulating Two Molecules of H2 (2008)
  • Author(s): M. Murata, S. Maeda, Y. Morinaka, Y. Murata, and K. Komatsu
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 15800-15801
  • Peer Reviewed
• [Journal Article] Demonstration of a Chemical Transformation Inside a Fullerene. The Reversible Conversion of the Allotropes of H2@C60. (2008)
  • Author(s): N. J. Turro, A. A. Marti, J. Y. -C. Chen, S. Jockusch, R. G. Lawler, M. Ruzzi, E. Sartori, S-C. Chuang, K. Komatsu and Y. Murata,
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 10506-10507
  • Peer Reviewed
• [Journal Article] NMR Studies on Monofunctionalized Fullerenyl Cation and Anion Encapsulating a H2 Molecule. (2008)
  • Author(s): M. Murata, Y, Ochi, T. Kitagawa, K. Komatsu, and Y. Murata
  • Journal Title: Chem. Asian J. 3 Pages: 1336-1342
  • Peer Reviewed
• [Journal Article] Encapsulation and Dynamic Behavior of Two H2 Molecules in an Open-Cage C70. (2008)
  • Author(s): Y. Murata, S. Maeda, M. Murata, and K. Komatsu.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 6702-6703
  • Peer Reviewed
• [Journal Article] Paramagnet Enhanced Nuclear Relaxation of H2 in Organic Solvents and in H2@C60. (2008)
  • Author(s): E. Sartori, M. Ruzzi, N. J. Turro, K. Komatsu, Y. Murata, R. G. Lawler, and A. L. Buchachenko
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 2221-2225
  • Peer Reviewed
• [Journal Article] Internal Magnetic Fields of Dianions of Fullerene C60 and Its Cage-Opened Derivatives Studied by Encapsulated H2 as an NMR Probe. (2008)
  • Author(s): M. Murata, Y. Ochi, F. Tanabe, K. Komatsu, and Y. Murata, Angew.
  • Journal Title: em. Int. Ed. 47 Pages: 2039-2041
  • Peer Reviewed
• [Journal Article] Can H2 Inside C60 Communicate with the Outside World? (2007)
  • Author(s): J. Lopez-Gejo, A. A. Marti, M. Ruzzi, S. Jockusch, K. Komatsu, Y. Murata, and N. J. Turro,
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 14554-14555
  • Peer Reviewed
• [Journal Article] Efficient Synthesis of Open-Cage Fullerene Derivatives Having 16-Membered-Ring Orifices. (2007)
  • Author(s): M. M. Roubelakis, Y. Murata, K. Komatsu, and M. Orfanopoulos
  • Journal Title: J. Org. Chem. 72 Pages: 7042-7045
  • Peer Reviewed
• [Journal Article] An Orifice-Size Index for Open-Cage Fullerenes. (2007)
  • Author(s): S-C. Chuang, Y. Murata, M. Murata, and K. Komatsu
  • Journal Title: J. Org. Chem. 72 Pages: 6447-6453
  • Peer Reviewed
• [Journal Article] The Outside Knows the Difference Inside : Trapping Helium by Immediate Reduction of Orifice Size of an Open-Cage Fullerene and the Effect of Encapsulated Helium and Hydrogen upon the NMR of Proton Directly Attached to the Outside (2007)
  • Author(s): S-C. Chuang, Y. Murata, M. Murata, and K. Komatsu
  • Journal Title: Chem. Commun. Pages: 1751-1753
  • Peer Reviewed
• [Journal Article] Fine Tuning of the Orifice Size of an Open-Cage Fullerene by Placing Selenium in the Rim : Insertion/Release of Molecular Hydrogen. (2007)
  • Author(s): S-C. Chuang, Y. Murata, M. Murata, S. Mori, S. Maeda, F. Tanabe, and K. Komatsu
  • Journal Title: Chem. Commun. Pages: 1278-1280
  • Peer Reviewed
• [Journal Article] Nuclear Relaxation of H2 and H2@C60 in Organic Solvents. (2006)
  • Author(s): E. Sartori, M. Ruzzi, N. J. Turro, J. D. Decatur, D. C. Doetschman, R. G. Lawler, A. L. Buchachenko, Y. Murata, and K. Komatsu
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 14752-14753
  • Peer Reviewed
• [Journal Article] (2006)
  • Author(s): M. Murata, Y. Murata, and K. Komatsu
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 8024-8033
  • Peer Reviewed
• [Journal Article] Cryogenic NMR Spectroscopy of Endohedral Hydrogen-Fullerene Complexes. (2006)
  • Author(s): M. Carravetta, O. G. Johannessen, M. H. Levitt, I. Heinmaa, R. Stern, A. Samoson, A. J. Horsewill, Y. Murata, and K. Komatsu
  • Journal Title: J. Chem. Phys. 124 Pages: 104507/1-104507/13
  • Peer Reviewed
• [Presentation] 2個の水素分子を内包したフラーレンC70 の[4+2]環化付加反応 (2009)
  • Author(s): 小松紘一(代表)
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-27
• [Presentation] Generation of Ionic [60]Fullerene Derivatives Encapsulating Molecular Hydrogen (2008)
  • Author(s): 小松紘一(代表)
  • Organizer: Pacific Rim Meeting on Electrochemical and Solid-State Science
  • Place of Presentation: Honolulu, U. S. A.
  • Year and Date: 2008-10-15
• [Presentation] Synthesis of Endohedral Open-Cage Fullerenes and Studies on Non-Covalent Interaction between Encapsulated Species and Fullerene Cage. (2008)
  • Author(s): 小松紘一(代表)
  • Organizer: The 213th Electrochemical Society Meeting
  • Place of Presentation: Phoenix, U. S. A.
  • Year and Date: 2008-05-20
• [Presentation] ラクトン構造をもつ新しい開口フラーレンの合成と性質 (2008)
  • Author(s): 小松紘一(代表)
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-27
• [Presentation] ビシクロ炭素骨格によって取囲まれたπ 電子系-ビシクロ[2.2.2]オクテンとビシクロ[2.1.1]ヘキセンの違い (2007)
  • Author(s): 小松紘一
  • Organizer: 有機π電子系シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2007-12-08
• [Presentation] Synthesis of Endohedral Open-Cage Fullerenes and Studies on Non-Covalent Interaction between Encapsulated Species and Fullerene Cage (2007)
  • Author(s): 小松紘一(代表)
  • Organizer: 12th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: 淡路
  • Year and Date: 2007-07-24
• [Presentation] Organic Chemistry of Fullerenes : Solid-State Reaction to Molecular Surgery (2007)
  • Author(s): 小松紘一(代表)
  • Organizer: The 15th European Symposium on Organic Chemistry
  • Place of Presentation: Dublin, Ireland
  • Year and Date: 2007-07-09
• [Presentation] Fine Tuning of the Orifice Size : Synthesis and Properties of Selenium-Containing Open-Cage C60 (2007)
  • Author(s): 小松紘一(代表)
  • Organizer: The 211th Electrochemical Society Meeting
  • Place of Presentation: Chicago, U. S. A.
  • Year and Date: 2007-05-14
• [Presentation] Organic Synthesis of Endohedral Fullerenes by Molecular Surgery (2006)
  • Author(s): 小松紘一
  • Organizer: The 10th International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: 京都
  • Year and Date: 2006-11-15
• [Presentation] 有機化学によるフラーレンの構造変換-固体反応から分子手術まで (2006)
  • Author(s): 小松紘一
  • Organizer: 有機合成化学協会中国四国支部特別講演会
  • Place of Presentation: 岡山
  • Year and Date: 2006-11-11
• [Presentation] 分子を手術して内包フラーレンをつくる (2006)
  • Author(s): 小松紘一
  • Organizer: 学術創成研究公開シンポジウム「物理と化学が生み出す未来物質」
  • Place of Presentation: 東京
  • Year and Date: 2006-11-04
• [Presentation] 有機化学によるフラーレンの構造変換-固体反応から分子手術まで- (2006)
  • Author(s): 小松紘一
  • Organizer: 機能物質化学セミナー
  • Place of Presentation: 相模
  • Year and Date: 2006-07-21
• [Presentation] Organic Synthesis of Endohedral Fullerenes Encapsulating Hydrogen Molecule(s) (2006)
  • Author(s): 小松紘一
  • Organizer: Forum for Molecular Science
  • Place of Presentation: 西安
  • Year and Date: 2006-06-30
• [Presentation] 炭素π共役系の極限的構造と物性に関する実験的研究 (2006)
  • Author(s): 小松紘一
  • Organizer: 日本化学会第86春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2006-03-28
• [Presentation] 分子手術法による水素内包フラーレン類の新規合成 (2006)
  • Author(s): 小松紘一
  • Organizer: 東京工業大学21世紀COE公開シンポジウム「分子多様性の創出と機能開拓」
  • Place of Presentation: 東京
  • Year and Date: 2006-01-28
• [Presentation] 新しい二次元および三次元π共役系の実現を目指して (2006)
  • Author(s): 小松紘一
  • Organizer: 有機合成新春講演会
  • Place of Presentation: 大阪
  • Year and Date: 2006-01-25
• [Book] ナノカーボンハンドブック (2007)
  • Author(s): 小松紘一,村田理尚
  • Total Pages: 594-598
  • Publisher: エヌティーエス出版
• [Book] Recent Developments in Carbocation and Onium Ion Chemistry (2007)
  • Author(s): K. Komatsu
  • Total Pages: 32-50
  • Publisher: ACS Symposium Series
• [Book] 化学:元素が彩る暮らしと未来 (2006)
  • Author(s): 小松紘一,クバプロ
  • Total Pages: 184-193
• [Book] Carbon-Rich Compounds‐From Molecules to Materials (2006)
  • Author(s): T. Kitagawa, Y. Murata, and K. Komatsu
  • Total Pages: 383-420
  • Publisher: Wiley-VCH Verlag