Creation of Paramagnetic Endofullerenes by Organic Synthesis

2013 Fiscal Year Final Research Report

• Project/Area Number: 24655027
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: MURATA Yasujiro 京都大学, 化学研究所, 教授 (40314273)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Keywords: 有機合成 / 常磁性 / 内包フラーレン

Research Abstract

The reaction of a tetraketo-open-cage C60 derivative with elemental sulfur in the presence of tetrakis(dimethylamino)ethylene afforded novel open C60 derivatives containing sulfur atom(s) in the rim of the orifice and the first example of an open C59S derivative. The single crystal X-ray analyses clearly determined these structures and demonstrated that a water molecule was encapsulated inside the cages. The orifice sizes were found to be large enough to insert N2 and O2 molecule inside the molecule. On the other hand, we conducted the X-ray diffraction study of He@C60 and the clear observation of a single helium atom inside C60. In addition, the close packing of a helium atom and a nitrogen atom inside fullerenes is realized using two stepwise insertion techniques, that is, molecular surgery to synthesize the fullerenes encapsulating a helium atom, followed by nitrogen radio-frequency plasma methods to generate the fullerenes encapsulating both helium and nitrogen atoms.

Research Products

• [Journal Article] Catalytic Stereodivergent Functionalization of H_2@C_<60> (2014)
  • Author(s): Maroto, E. E.; Izquierdo, M.; Filippone, S.; Murata, M.; Murata, Y.; Komatsu, K.; Martin
  • Journal Title: N. Chem. Commun Volume: 50 Pages: 740-742
  • DOI: 10.1039/c3cc46999a
  • Peer Reviewed
• [Journal Article] Cubic Dipole Lattice of Water Molecules Trapped inside Carbon Cages (2014)
  • Author(s): Aoyagi, S.; Hoshino, N.; Akutagawa, T.; Sado, Y.; Kitaura, R.; Shinohara, H.; Sugimoto, K.; Zhang, R.; Murata
  • Journal Title: Y. Chem. Commun Volume: 50 Pages: 524-526
  • DOI: 10.1039/C3CC46683C
  • Peer Reviewed
• [Journal Article] Paramagnet Enhanced Nuclear Spin Relaxation in H_2O@Open-C_<60> and H_2@Open-C_<60> (2013)
  • Author(s): Li, Y.; Lei, X.; Chen, J. Y.-C.; Murata, Y.; Turro, N. J.; Lawler
  • Journal Title: R. G. Org. Lett. Volume: 15 Pages: 4746-4749
  • DOI: 10.1021/ol402111x
  • Peer Reviewed
• [Journal Article] Nuclear Magnetic Resonance of Hydrogen Molecules Trapped inside C_<70> Fullerene Cages (2013)
  • Author(s): Mamone, S.; Concistre, M.; Heinmaa, I.; Carravetta, M.; Kuprov, I.; Wall, G.; Denning, M.; Lei, X.; Chen, J. Y.-C.; Li, Y.; Murata, Y.; Turro, N. J.; Levitt
  • Journal Title: M. H. ChemPhysChem Volume: 14 Pages: 3121-3130
  • DOI: 10.1002/cphc.201300269
  • Peer Reviewed
• [Journal Article] Nuclear Spin Isomers of Guest Molecules in H_2@C_<60>, H_2O@C_<60> and Other Endofullerenes (2013)
  • Author(s): Chen, J. Y.-C.; Li, Y.; Frunzi, M.; Lei, X.; Murata, Y.; Lawler, R.G.; Turro, N. J. Phil
  • Journal Title: Trans. R. Soc. Volume: 371,20120429 Pages: 16
  • DOI: 10.1098/rsta.2012.0429
  • Peer Reviewed
• [Journal Article] Assessment of Fullerene Derivatives as Rolling Journals in a Finite Carbon Nanotube Bearing (2013)
  • Author(s): Hitosugi, S.; Iizuka, R.; Yamasaki, T.; Zhang, R.; Murata, Y.; Isobe
  • Journal Title: H. Org. Lett. Volume: 15 Pages: 3199-3201
  • DOI: 10.1021/ol400982r
  • Peer Reviewed
• [Journal Article] Synthesis and X-Ray Structure of Endohedral Fullerene C_<60> Dimer Encapsulating a Water Molecule in Each C_<60> Cage (2013)
  • Author(s): Zhang, R.; Murata, M.; Wakamiya, A.; Murata
  • Journal Title: Y. Chem. Lett. Volume: 42 Pages: 879-881
  • DOI: 10.1246/cl.130358
  • Peer Reviewed
• [Journal Article] Expansion of Orifices of Open C_<60> Derivatives and Formation of an Open C_<59>S Derivative by Reaction with Sulfur (2013)
  • Author(s): Futagoishi, T.; Murata, M.; Wakamiya, A.; Sasamori, T.; Murata
  • Journal Title: Y. Org. Lett. Volume: 15 Pages: 2750-2753
  • DOI: 10.1021/ol401083c
  • Peer Reviewed
• [Journal Article] Synthesis and Photovoltaic Properties of Bulky Acceptor Materials Based on the Dimerization of Fullerene C_<60> for Efficient Polymer Solar Cells (2013)
  • Author(s): Morinaka, Y.; Nobori, M.; Murata, M.; Wakamiya, A.; Sagawa, T.; Yoshikawa, S.; Murata
  • Journal Title: Y. Chem. Commun Volume: 49 Pages: 3670-3672
  • DOI: 10.1039/C3CC41084F
  • Peer Reviewed
• [Journal Article] X-Ray Observation of a Helium Atom and Placing a Nitrogen Atom inside He@C_<60> and He@C_<70> (2013)
  • Author(s): Morinaka, Y.; Sato, S.; Wakamiya, A.; Nikawa, H.; Mizorogi, N.; Tanabe, F.; Murata, M.; Komatsu, K.; Furukawa, K.; Kato, T.; Nagase, S.; Akasaka, T.; Murata
  • Journal Title: Y. Nat. Commun Volume: 4,1554 Pages: 5
  • DOI: 10.1038/ncomms2574
  • Peer Reviewed
• [Journal Article] Synthesis, Isomer Count, and Nuclear Spin Relaxation of H_2O@Open-C_<60> Nitroxide Derivatives (2012)
  • Author(s): Li, Y.; Lei, X.; Lawler, R. G.; Murata, Y.; Komatsu, K.; Turro
  • Journal Title: N. J. Org. Lett. Volume: 14 Pages: 3822-3825
  • DOI: 10.1021/ol3013155
  • Peer Reviewed
• [Journal Article] Quantum Rotation of Ortho and Para-water Encapsulated in a Fullerene Cage (2012)
  • Author(s): Beduz, C.; Carravetta, M.; Chen, J. Y.-C.; Concistre, M.; Denning, M.; Frunzi, M.; Horsewill, A. J.; Johannessen, O. G.; Lawler, R.; Lei, X.; Levitt, M. H.; Li, Y.; Mamone, S.; Murata, Y.; Nagel, U.; Nishida, T.; Ollivier, J.; Rols, S.; Room, T.; Sarker, R.; Turro, N. J.; Yang
  • Journal Title: Y. Proc. Natl. Acad. Sci. USA Volume: 109 Pages: 12894-12898
  • DOI: 10.1073/pnas.1210790109
  • Peer Reviewed
• [Journal Article] ENDOR Evidence of Electron-H_2 Interaction in a Fulleride Embedding H_2 (2012)
  • Author(s): Zoleo, A.; Lawler, R.; Lei, X.; Li, Y.; Murata, Y.; Komatsu, K.; Valentin, M. D.; Ruzzi, M.; Turro
  • Journal Title: N. J. J. Am. Chem. Soc. Volume: 134 Pages: 12881-12884
  • DOI: 10.1021/ja211944q
  • Peer Reviewed
• [Presentation] フラーレンC_<60>のケトラクタム誘導体における開口部拡大反応 (2014)
  • Author(s): 橋川祥史, 他
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
  • Year and Date: 20140327-30
• [Presentation] ケトラクタム構造をもつ新しい開口C_<60>誘導体の合成 (2014)
  • Author(s): 橋川祥史, 他
  • Organizer: 第45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: 東京大学伊藤謝恩ホール
  • Year and Date: 20140303-05
• [Presentation] X-ray Structure and Reaction of a Precursor for Endohedral C_<59>N (2014)
  • Author(s): Yoshifumi Hashikawa, 他
  • Organizer: Institute for Chemical Research International Symposium 2014
  • Place of Presentation: Obaku Plaza, Kyoto University, Uji, Japan
  • Year and Date: 2014-10-12
• [Presentation] 水内包フラーレンC_60の二量化とX線構造 (2013)
  • Author(s): 張鋭, 他
  • Organizer: 第9回有機元素化学セミナー
  • Place of Presentation: 京都大学宇治キャンパスきはだホール
  • Year and Date: 20131129-30
• [Presentation] Organic Synthesis of Endohedral Fullerenes and Their Reactions (2013)
  • Author(s): Yasujiro Murata
  • Organizer: 5th International Symposium on Emergence of Highly Elavoratedπ-Space and Its Function
  • Place of Presentation: Okazaki Conference Center, Higashiokazaki, Japan
  • Year and Date: 20131024-25
• [Presentation] Novel Endohedral Fullerenes : Synthesis and Reactions (2013)
  • Author(s): Yasujiro Murata
  • Organizer: The Third Symposium on "Carbon Nanoforms"
  • Place of Presentation: Madrid Institute for Advanced Studies in Nanoscience, Madrid, Spain
  • Year and Date: 20130926-27
• [Presentation] 水分子内包フラーレンの結晶構造と誘電的性質 (2013)
  • Author(s): 青柳忍, 他
  • Organizer: 本物理学会2013年秋期大会
  • Place of Presentation: 徳島大学
  • Year and Date: 20130925-28
• [Presentation] 硫黄挿入反応を利用した新規開口C_<60>誘導体の合成と小分子内包体のX線構造 (2013)
  • Author(s): 二子石師, 他
  • Organizer: 第24回基礎有機化学討論会
  • Place of Presentation: 学習院大学目白キャンパス
  • Year and Date: 20130905-07
• [Presentation] H_2O@C_<60>の固体反応ならびに[2+2]型二量体のX線構造 (2013)
  • Author(s): 張鋭, 他
  • Organizer: 第45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: 大阪大学
  • Year and Date: 20130805-07
• [Presentation] Synthesis and Reactions of Novel Endohedral Fullerenes (2013)
  • Author(s): Yasujiro Murata, 他
  • Organizer: 15th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Taipei, Taiwan
  • Year and Date: 20130728-0802
• [Presentation] ヘリウム原子と窒素原子を内包したフラーレンの発生 (2013)
  • Author(s): 村田靖次郎, 他
  • Organizer: 新学術領域研究「高次π空間の創発と機能開発」第9回公開シンポジウム
  • Place of Presentation: シーサイドホテル舞子ビラ神戸、神戸
  • Year and Date: 20130313-14
• [Presentation] ヘリウム内包フラーレンの有機合成ならびに2つの異種原子を内包したフラーレンの発生 (2013)
  • Author(s): 森中裕太, 他
  • Organizer: 第44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: 東京大学伊藤国際学術研究センター謝恩ホール
  • Year and Date: 20130311-13
• [Presentation] Recent Progress on the Synthesis and Reaction of Novel Endofullerenes (2013)
  • Author(s): Yasujiro Murata
  • Organizer: A Life in Science : A Meeting on Endofullerene Molecular Systems in Memory of Nicholas J. Turro
  • Place of Presentation: Department of Chemistry, Columbia University, New York, USA
  • Year and Date: 2013-05-12
• [Presentation] 小分子内包フラーレンの有機合成 (2012)
  • Author(s): 村田靖次郎, 他
  • Organizer: 奈良先端未来開拓コロキウム2012～分子、超分子から分子技術の時代へ～
  • Place of Presentation: 学際融合領域研究棟1号館1階「交流・カンファレンスルーム」、奈良先端科学技術大学院大学、奈良
  • Year and Date: 20121207-08
• [Presentation] Synthesis and Photophysical Properties of Azafullerenes Directly Connected to an Organic Dye (2012)
  • Author(s): Yasujiro Murata, 他
  • Organizer: 4th International Symposium on Emergence of Highly Elaboratedπ-Space and Its Function
  • Place of Presentation: Hamanako Royal Hotel, Hamamatsu, Japan
  • Year and Date: 20121113-14
• [Presentation] Synthesis and Photovoltaic Properties of Dumbbell-Shaped Fullerene Derivatives (2012)
  • Author(s): Michihisa Murata, 他
  • Organizer: The Twelfth International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: Rihga Royal Hotel Kyoto, Kyoto, Japan
  • Year and Date: 20121112-16
• [Presentation] ダンベル型フラーレン誘導体 : 有機薄膜太陽電池のモルフォロジー制御 (2012)
  • Author(s): 村田理尚, 他
  • Organizer: 23回基礎有機化学討論会
  • Place of Presentation: 京都テルサ、京都
  • Year and Date: 20120919-21
• [Presentation] Synthesis of Endohedral Fullerene C_<60> Encapsulating a Single Molecule of Water (2012)
  • Author(s): Kei Kurotobi, 他
  • Organizer: 第43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: 東北大学百周年記念会館川内萩ホール
  • Year and Date: 20120905-07
• [Presentation] 17員環開口部をもつ新規フラーレン誘導体の合成と性質 (2012)
  • Author(s): 村田靖次郎, 他
  • Organizer: 新学術領域研究「高次π空間の創発と機能開発」第8回公開シンポジウム
  • Place of Presentation: ホテルアローレ、加賀
  • Year and Date: 20120719-20
• [Presentation] ダンベル型フラーレン誘導体の合成と光電変換特性 (2012)
  • Author(s): 村田理尚, 他
  • Organizer: 日本学術振興会産学協力研究委員会第9回「次世代の太陽光発電システム」シンポジウム
  • Place of Presentation: 京都テルサ
  • Year and Date: 20120531-0601
• [Presentation] Synthesis of Endohedral C_<60> Encapsulating a Water Molecule (2012)
  • Author(s): Yasujiro Murata, 他
  • Organizer: The 10th International Conference on Heteroatom Chemistry (ICHAC-10)
  • Place of Presentation: Obaku Plaza, Kyoto University, Kyoto, Japan
  • Year and Date: 20120520-25
• [Book] Organic Synthesis of Endohedral Fullerenes Encapsulating Helium, Dihydrogen, and Water (2013)
  • Author(s): Murata, M.; Murata, Y.; Komatsu, K. Organic Nanomaterials, Torres, T., Bottari, G. Eds
  • Total Pages: 225-240
  • Publisher: Wiley-Blackwell, Oxford
• [Book] CSJカレントレビュー「未来材料を創出するπ電子系の科学」 (2013)
  • Author(s): 村田靖次郎
  • Total Pages: 70-76
  • Publisher: 化学同人
• [Book] 高次π空間の創発と機能開発 (2013)
  • Author(s): 村田靖次郎
  • Total Pages: 64-67
  • Publisher: シーエムシー出版
• [Remarks]
  • URL: http://www.scl.kyoto-u.ac.jp/~kouzou/index.html