Synthesis of Three Dimensional π-Systems with Bowl Structures by the Top-down Approach and Developments of Their Functions

• Project/Area Number: 20681009
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Nanostructural science
• Research Institution: Kyoto University
• Principal Investigator: MURATA Yasujiro Kyoto University, 化学研究所, 教授 (40314273)
• Co-Investigator(Renkei-kenkyūsha): MURATA Michihisa 京都大学, 化学研究所, 助教 (30447932) ; WAKAMIYA Atsushi 京都大学, 化学研究所, 准教授 (60362224)
• Project Period (FY): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥24,830,000 (Direct Cost: ¥19,100,000、Indirect Cost: ¥5,730,000); Fiscal Year 2010: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000); Fiscal Year 2009: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000); Fiscal Year 2008: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000)
• Keywords: ボウル型分子 / 3次元π共役系 / 開口フラーレン / 酸化還元電位 / 有機薄膜太陽電池 / 小分子内包 / フラーレン / 三次元π共役 / 内包フラーレン / 3次元π共役 / 酸化反応 / HOMO-LUMOギャップ

Research Abstract

Novel functional organic compounds having a bowl-shaped structure with three dimensional π-system were synthesized by the top-down approach from fullerenes. The synthetic methods for cleavage of the σ- and π-bonds of fullerenes were developed. The redox properties were controlled by chemical modification of the functional groups at the rim of the molecules. It was revealed that the material gives higher open-circuit voltage when used for organic thin-layer photovoltaic devices. Furthermore, it was possible to encapsulate a small molecule inside the π-system.

Research Products

• [Journal Article] Interaction potential and infrared absorption of endohedral H2 in C60 (2011)
  • Author(s): Ge, M.; Nagel, U.; Huevonen, D.; Room, T.; Mamone, S.; Carravetta, M.; Levitt, M.H.; Murata, Y.; Komatsu, K.; Chen, J.Y.-C.; Turro, N.J.
  • Journal Title: J.Chem.Phys. Volume: 134
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Bispyrrolidine Derivatives of H2@C60 : Differentiation of Isomers using 1H NMR Spectroscopy of Endohedral H2 (2011)
  • Author(s): Li, Y.; Lei, X.; Lawler, R.G.; Murata, Y.; Komatsu, K.; Turro, N.J.
  • Journal Title: Chem.Commun. Volume: 47 Pages: 2282-2284
  • Peer Reviewed
• [Journal Article] Modification of σ-Framework of[60]Fullerene for Bulk-heterojunction Solar Cells (2010)
  • Author(s): Murata M. ; Morinaka Y. ; Murata Y. ; Yoshikawa O. ; Sagawa T. ; Yoshikawa S.
  • Journal Title: Chem.Commun. in press Pages: 47-47
  • NAID: 120004225593
  • Peer Reviewed
• [Journal Article] Rational Synthesis, Enrichment, and 13C NMR Spectra of Endohedral C60 and C70 Encapsulating a Helium Atom (2010)
  • Author(s): Morinaka Y. ; Tanabe F. ; Murata M. ; Murata Y. ; Komatsu K.
  • Journal Title: Chem.Commun. 46 Pages: 4532-4534
  • Peer Reviewed
• [Journal Article] Reaction of Cage-Opened Fullerene Derivative with Grignard Reagents and Subsequent Transannular Cyclization (2010)
  • Author(s): Murata M. ; Morinaka Y.; Kurotobi K.; Komatsu K.; Murata Y.
  • Journal Title: Chem.Lett. 39 Pages: 298-299
  • NAID: 10027178725
  • Peer Reviewed
• [Journal Article] A Magnetic Switch for Spin Catalyzed Interconversion of Nuclear Spin Isomers (2010)
  • Author(s): Li Y. ; Lei X. ; Jockusch S. ; Chen J.Y.-C. ; Frunzi M. ; Johnson J.A. ; Lawler R.G. ; Murata Y. ; Murata M. ; Komatsu K. ; Turro N.
  • Journal Title: J.Am.Chem.Soc. 132 Pages: 4042-4043
  • Peer Reviewed
• [Journal Article] A Magnetic Switch for Spin Catalyzed Interconversion of Nuclear Spin Isomers (2010)
  • Author(s): Li, Y.; Lei, X.; Jockusch, S.; Chen, J.Y.-C.; Frunzi, M.; Johnson, J.A.; Lawler, R.G.; Murata, Y.; Murata, M.; Komatsu, K.; Turro, N.
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 4042-4043
  • Peer Reviewed
• [Journal Article] Rational Synthesis, Enrichment, and 13C NMR Spectra of Endohedral C60 and C70 Encapsulating a Helium Atom (2010)
  • Author(s): Morinaka, Y.; Tanabe, F.; Murata, M.; Murata, Y.; Komatsu, K.
  • Journal Title: Chem.Commun. Volume: 46 Pages: 4532-4534
  • Peer Reviewed
• [Journal Article] Magnetic Interaction of Solution-State Paramagnets with Encapsulated H2O and H2 (2010)
  • Author(s): Frunzi, M.; Lei, X.; Murata, Y.; Komatsu, K.; Iwamatsu, S-i.; Murata, S.; Lawler, R.G.; Turro, N.J.
  • Journal Title: J.Phys.Chem.Lett. Volume: 1 Pages: 1420-1422
  • Peer Reviewed
• [Journal Article] Inelastic neutron scattering of a quantum translator-rotator encapsulated in a closed fullerene cage : Isotope effects and translation-rotation coupling in H2@C60 and HD@C60 (2010)
  • Author(s): Horsewill, A.J.; Rols, S.; Johnson, M.R.; Murata, Y.; Murata, M.; Komatsu, K.; Carravetta, M.Mamone, S.; Levitt, M.H.; Chen, J.Y-C.; Johnson, J.A.; Lei, X.; Turro, N.J.
  • Journal Title: Phys.Rev.B Volume: 82
  • Peer Reviewed
• [Journal Article] Comparative NMR Properties of H2 & HD in Toluene-d8 and in H2/HD@C60 (2010)
  • Author(s): Chen, J.Y.-C.; Marti, A.A.; Turro, N.J.; Komatsu, K.; Murata, Y.; Lawler, R.G.
  • Journal Title: J.Phys.Chem.B Volume: 114 Pages: 14689-14695
  • Peer Reviewed
• [Journal Article] The Spin Chemistry and Magnetic Resonance of H2@C60. From the Pauli Principle to Trapping a Long Lived Nuclear Excited Spin State Inside a Buckyball (2010)
  • Author(s): Turro, N.; Chen, J.Y.-C.; Satori, E.; Ruzzi, M.; Marti, A.; Lawler, R.; Jockusch, S.; Lopez-Gejo, J.; Komatsu, K.; Murata, Y.
  • Journal Title: Acc.Chem.Res. 43 Pages: 335-345
  • Peer Reviewed
• [Journal Article] A Magnetic Switch for Spin Catalyzed Interconversion of Nuclear Spin Isomers (2010)
  • Author(s): Li, Y.; Lei, X.; Jockusch, S.; Judy, C.; Frunzi, M.; Johnson, J.; Lawler, R.; Murata, Y.; Murata, M.; Komatsu, K.; Turro, N.
  • Journal Title: J.Am.Chem.Soc. 132 Pages: 4042-4043
  • Peer Reviewed
• [Journal Article] Quantum Translator-Rotator: Inelastic Neutron Scattering of Dihydrogen Molecules Trapped inside Anisotropic Fullerene Cages (2009)
  • Author(s): Horsewill,A.J. ; Panesar K.S. ; Rols S. ; Johnson M.R. ; Murata Y. ; Komatsu K. ; Mamone S. ; Danquigny A. ; Cuda F. ; Maltsev S. ; Grossel M.C. ; Carravetta M. ; Levitt M.H.
  • Journal Title: Phys.Rev.Lett. 102
  • Peer Reviewed
• [Journal Article] Rigid Alicyclic Molecules from Bicyclo[2.2.1]hept-2-enes (=8,9,10-Trinorbornenes) and 1,4-Dipyridin-2-ylphthalazines as Stereoselective Coupling Agents (2009)
  • Author(s): Margetic, D.; Murata, Y.; Komatsu, K.; Marinic, Z.
  • Journal Title: Helv.Chim.Acta 92 Pages: 298-312
  • Peer Reviewed
• [Journal Article] Quantum Translator-Rotator : Inelastic Neutron Scattering of Dihydrogen Molecules Trapped inside Anisotropic Fullerene Cages (2009)
  • Author(s): Horsewill, A.J.; Panesar, K.S.; Rols, S.; Johnson, M.R.; Murata, Y.; Komatsu, K.; Mamone, S.; Danquigny, A.; Cuda, F.; Maltsev, S.; Grossel, M.C.; Carravetta, M.; Levitt, M.H.
  • Journal Title: Phys.Rev.Lett. 102
  • Peer Reviewed
• [Journal Article] Rotor in a Cage : Infrared Spectroscopy of an Endohedral Hydrogen-fullerene Complex (2009)
  • Author(s): Mamone, S.; Ge, M.; Huevonen, D.; Nagel, U.; Danquigny, A.; Cuda, F.; Grossel, M.C.; Murata, Y.; Komatsu, K.; Levitt, M.H.; Room, T.; Caravetta, M.
  • Journal Title: J.Chem.Phys. 130
  • Peer Reviewed
• [Journal Article] Rotational Sublevels of an Ortho-Hydrogen Molecule Encapsulated in an Isotropic C60 Cage (2009)
  • Author(s): Kohama, Y.; Rachi, T.; Jing, J.; Li, Z.; Tang, J.; Kumashiro, R.; Izumisawa, S.; Kawaji, H.; Atake, T.; Sawa, H.; Murata, Y.; Komatsu, K.; Tanigaki, K.
  • Journal Title: Phys.Rev.Lett. 103
  • NAID: 120002086073
  • Peer Reviewed
• [Journal Article] Reaction of Cage-Opened Fullerene Derivative with Grignard Reagents and Subsequent Transannular Cyclization (2009)
  • Author(s): Murata, M.; Morinaka, Y.; Kurotobi, K.; Komatsu, K.; Murata, Y.
  • Journal Title: Chem.Lett. 39 Pages: 298-299
  • NAID: 10027178725
  • Peer Reviewed
• [Journal Article] Encapsulation and Dynamic Behavior of Two H2 Molecules in an Open-Cage C70 (2008)
  • Author(s): Murata Y. ; Maeda S. ; Murata M. ; Komatsu K.
  • Journal Title: J.Am.Chem.Soc. 130 Pages: 6702-6703
  • Peer Reviewed
• [Journal Article] Synthesis and Reaction of Fullerene C70 Encapsulating Two Molecules of H2 (2008)
  • Author(s): Murata M. ; Maeda S. ; Morinaka Y. ; Murata Y. ; Komatsu K.
  • Journal Title: J.Am.Chem.Soc. 130 Pages: 15800-15801
  • 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): Murata, M. ; Ochi, Y. ; Tanabe, F. ; Komatsu, K. ; Murata, Y.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 2039-2041
  • Peer Reviewed
• [Journal Article] Encapsulation and Dynamic Behavior of Two H2 Molecules in an Open-Cage C70 (2008)
  • Author(s): Murata, Y. ; Maeda ; S. ; Murata, M. ; Komatsu, K.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 6702-6703
  • Peer Reviewed
• [Journal Article] Synthesis and Reaction of Fullerene C70 Encapsulating Two Molecules of H2 (2008)
  • Author(s): Murata, M. ; Maeda, S. ; Morinaka, Y. ; Murata, Y. ; Komatsu, K.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 15800-15801
  • Peer Reviewed
• [Presentation] Organic Synthesis of Endohedral Fullerenes (2010)
  • Author(s): Yasujiro Murata
  • Organizer: Pacifichem 2010
  • Place of Presentation: Honolulu, USA(依頼講演)
  • Year and Date: 2010-12-15
• [Presentation] Organic Synthesis of Endohedral Fullerenes (2010)
  • Author(s): Yasujiro Murata
  • Organizer: Pacifichem 2010
  • Place of Presentation: Honolulu, Hawaii, U.S.A.(招待講演)
  • Year and Date: 2010-12-15
• [Presentation] σ-Framework Transformation of Fullerenes (2010)
  • Author(s): Yasujiro Murata
  • Organizer: Fullerene Silver Anniversary Symposium
  • Place of Presentation: Crete, Greece(依頼講演)
  • Year and Date: 2010-10-09
• [Presentation] δ-Framework Transformation of Fullerenes (2010)
  • Author(s): Yasujiro Murata
  • Organizer: Fullerene Silver Anniversary Symposium
  • Place of Presentation: Crete, Greece(招待講演)
  • Year and Date: 2010-10-09
• [Presentation] Organic Synthesis and Properties of H2@C60, H2@C70, and H2O@C60 (2010)
  • Author(s): Yasujiro Murata
  • Organizer: Japan-China Joint Symposium on Functional Supramolecular Architectures
  • Place of Presentation: Changchun, P.R.China(招待講演)
  • Year and Date: 2010-07-26
• [Presentation] Synthesis of Endohedral Fullerenes Encapsulating a Small Molecule (2010)
  • Author(s): Yasujiro Murata
  • Organizer: The 1st China-Japan Young Scientist Forum
  • Place of Presentation: Xiamen, China(依頼講演)
  • Year and Date: 2010-06-20
• [Presentation] Synthesis of Endohedral Fullerenes Encapsulating a Small Molecule (2010)
  • Author(s): Yasujiro Murata
  • Organizer: The 1st China-Japan Young Scientist Forum
  • Place of Presentation: Xiamen, P.R.China(招待講演)
  • Year and Date: 2010-06-20
• [Presentation] Organic Synthesis of an Endohedral C60 Encapsulating a Small Molecule (2010)
  • Author(s): Kei Kurotobi, Yasujiro Murata
  • Organizer: 217th ECS Meeting
  • Place of Presentation: Vancouver, Canada(依頼講演)
  • Year and Date: 2010-04-28
• [Presentation] Organic Synthesis of an Endohedral C60 Encapsulating a Small Molecule (2010)
  • Author(s): Kei Kurotobi, Yasujiro Murato
  • Organizer: 217th ECS Meeting
  • Place of Presentation: Vancouver, Canada(招待講演)
  • Year and Date: 2010-04-28
• [Presentation] 水分子内包フラーレンC60の有機合成 (2010)
  • Author(s): 黒飛敬、村田靖次郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
  • Year and Date: 2010-03-28
• [Presentation] チオフェンをもつ新規π共役拡張型開口フラーレンの合成 (2010)
  • Author(s): 保井秀文、黒飛敬、村田靖次郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
  • Year and Date: 2010-03-28
• [Presentation] グリニャール試薬を用いた開口フラーレンの構造変換 (2010)
  • Author(s): 森田裕太、村田理尚、黒飛敬、小松紘一、村田靖次郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
  • Year and Date: 2010-03-28
• [Presentation] フラーレンC70の二価アニオン種の発生と骨格内の磁気的性質 (2010)
  • Author(s): 登政博、村田理尚、小松紘一、村田靖次郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
  • Year and Date: 2010-03-28
• [Presentation] ピロール環が直結したアザフラーレン誘導体の合成と性質 (2010)
  • Author(s): 勝谷郷史、村田理尚、村田靖次郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿近学本部キャンパス
  • Year and Date: 2010-03-28
• [Presentation] 小分子内包フラーレンの有機合成 (2010)
  • Author(s): 村田靖次郎
  • Organizer: 第38回フラーレン・ナノチューブ総合シンポジウム
  • Place of Presentation: 名城大学(依頼講演)
  • Year and Date: 2010-03-03
• [Presentation] Organic Synthesis of Endofullerenes Encapsulating a Small Molecule (2010)
  • Author(s): Yasujiro Murata
  • Organizer: The 38th Fullerenes-Nanotube General Symposium
  • Place of Presentation: 名城大学
  • Year and Date: 2010-03-03
• [Presentation] Synthesis and Reaction of Fullerene C70 Encapsulating Two Molecules of H2 (2009)
  • Author(s): Michihisa Murata, Shuhei Maeda, Yuta Morinaka, Yasujiro Murata, Koichi Komatsu
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-11)
  • Place of Presentation: Rihga Royal Hotel Kyoto
  • Year and Date: 2009-11-12
• [Presentation] Synthesis and Properties of Novel Open-Cage C60 Derivatives (2009)
  • Author(s): Kei Kurotobi, Michihisa Murata, Yasujiro Murata
  • Organizer: The 11th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-11)
  • Place of Presentation: Rihga Royal Hotel Kyoto
  • Year and Date: 2009-11-12
• [Presentation] 水素分子を2個内包したフラーレンC70の[4+2]環化付加反応 (2009)
  • Author(s): 森中裕太、村田理尚、村田靖次郎、小松紘一
  • Organizer: 第20回基礎有機化学討論会
  • Place of Presentation: 群馬大学工学部桐生キャンパス
  • Year and Date: 2009-09-29
• [Presentation] Synthesis and Reaction of Fullerene C70 Encapsulating Two Molecules of H2 (2009)
  • Author(s): Michihisa Murata, Shuhei Maeda, Yuta Morinaka, Yasujiro Murata, Koichi Komatsu
  • Organizer: 第37回フラーレン・ナノチューブ総合シンポジウム
  • Place of Presentation: つくば国際会議場
  • Year and Date: 2009-09-03
• [Presentation] Synthesis and Properties of Novel Open-Cage C60 Derivatives (2009)
  • Author(s): Kei Kurotobi, Michihisa Murata, Yasujiro Murata
  • Organizer: 第37回フラーレン・ナノチューブ総合シンポジウム
  • Place of Presentation: つくば国際会議場
  • Year and Date: 2009-09-03
• [Presentation] Synthesis of Endohedral Open-Cage Fullerenes and Studies on Non-Covalent Interaction between Encapsulated Species and Fullerene Cage (2008)
  • Author(s): Yasujiro Murata, Shih-Ching Chuang, Michihisa Murata, Koichi Komatsu
  • Organizer: 213th ECS Meeting
  • Place of Presentation: Phoenix, Arizona USA
  • Year and Date: 2008-05-19
• [Book] Chemistry of Nanocarbons(Molecular Surgery toward Organic Synthesis of Endohedral Fullerenes)(F.Wudl, S.Nagase, T.Akasaka, Eds.) (2010)
  • Author(s): Michihisa Murata, Yasujiro Murata, Koichi Komatsu
  • Publisher: Wiley-Blackwell, Oxford
• [Remarks] ホームページ
  • URL: http://www.scl.kyoto-u.ac.jp/~kouzou/index.html
• [Patent(Industrial Property Rights)] 有機色素材料およびそれを用いた色素増感型太陽電池 (2011)
  • Inventor(s): 若宮淳志、谷口拓弘、村田靖次郎、ジョアン・ティング・ディ、瀬川浩司
  • Industrial Property Rights Holder: 国立大学法人京都大学
  • Industrial Property Number: 2011-053597
  • Filing Date: 2011-03-10
• [Patent(Industrial Property Rights)] 新規化合物、電荷輸送材料および有機デバイス (2011)
  • Inventor(s): 若宮淳志、西村秀隆、村田靖次郎、福島達也、梶弘典
  • Industrial Property Rights Holder: 国立大学法人京都大学、国立大学法人九州大学
  • Industrial Property Number: 2011-046888
  • Filing Date: 2011-03-03