Construction of supramolecular system based on paramagnetic endohedral metallofullerene

2008 Fiscal Year Final Research Report

• Project/Area Number: 19750025
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: University of Tsukuba
• Principal Investigator: TSUCHIYA Takahiro University of Tsukuba, 大学院・数理物質科学研究科, 講師 (10375412)
• Project Period (FY): 2007 – 2008
• Keywords: 金属内包フラーレン / 錯体 / 超分子 / 電子移動

Research Abstract

本研究は優れた電子受容性、供与性を示し、さらに磁性化、反磁性化の制御も容易な金属内包フラーレンに着目し、有機ドナー分子との超分子系の構築に関する検討を行った。具体的には、La_2@C_<80>と有機ドナー分子TMPDとの溶液中での挙動について検討を行ったところ、両者は電子移動を伴い錯体を形成することが分かった。興味深いことに、この電子移動は溶媒の誘電率や温度を変化させることによって可逆的にコントロール出来ることが分かった。

Research Products

• [Journal Article] Radical Coupling Reaction of Paramagnetic Endohedral Metallofullerene La@C_<82> (2008)
  • Author(s): Y. Maeda, A. Sagara, M. Hashimoto, Y. Hirashima, K. Sode, T. Hasegawa, M. Kanda, M. O. Ishitsuka, T. Tsuchiya, T. Akasaka, T. Okazaki, H. Kataura, J. Lu, S. Nagase, S. Takeuchi
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 16224-16230
  • Peer Reviewed
• [Journal Article] Does Gd@C_<82> 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] Chemical Understanding of a Non-IPR Metallofullerene : Stabilization of Encaged Metals on Fused-pentagon Bonds in La_2@C_^<72> (2008)
  • Author(s): X. Lu, H. Nikawa, T. Nakahodo, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, M. Toki, H. Sawa, Z. Slanina, N. Mizorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 9129-9136
  • 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] Addition of Adamantylidene to La_2@C_<78>: Isolation and Single Crystal X-ray Structural Determination of the Monoadducts (2008)
  • Author(s): B. Cao, H. Nikawa, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, H. Sawa, Z. Slanina, N. Mizorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 983-989
  • Peer Reviewed
• [Journal Article] Metal Atoms Collinear with the Spiro Carbon of 6, 6-Open Adducts, M_2@C_<80>(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] Bis-carbene Adducts of Non-IPR La_2@C_<72> : Localization of High Reactivity around Fused-pentagons and Toward Controllable Tuning of Electrochemical Properties of Metallofullerenes (2008)
  • Author(s): X. Lu, H. Nikawa, T. Tsuchiya, Y. Maeda, M. O. Ishitsuka, T. Akasaka, M. Toki, H. Sawa, Z. Slanina, N. Mizorogi, S. Nagase
  • Journal Title: Angew. Chem., Int. Ed. 47 Pages: 8642-8645
  • Peer Reviewed
• [Journal Article] Observation of ^<13>C NMR Chemical Shifts of Metal Carbides Encapsulated in Fullerenes : Sc_2C_2@C_<82>, Sc_2C_2@C_<84>, and Sc_3C_2@C_<80> (2008)
  • Author(s): Y. Yamazaki, K. Nakajima, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, M. Waelchili, N. Mizorogi, S. Nagase
  • Journal Title: Angew. Chem., Int. Ed. 47 Pages: 7905-7908
  • Peer Reviewed
• [Journal Article] [2+1]-Cycloaddition of Nitrene onto C_<60> Revisited : Interconversion between Aziridinofullerene and Azafulleroid (2008)
  • Author(s): T. Nakahodo, M. Okada, H. Morita, T. Yoshimura, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, H. Fujihara, T. Akasaka, X. Gao, S. Nagase
  • Journal Title: Angew. Chem., Int. Ed. 47 Pages: 1298-1300
  • Peer Reviewed
• [Journal Article] Location of the Metal Atoms in Ce_2@C_<78> 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] Molecular Transformations of Unsaturated Thiacrown Ethers (2008)
  • Author(s): T. Tsuchiya, Y. Okada, T. Shimizu, K. Hirabayashi, N. Kamigata
  • Journal Title: J. Org. Chem. 73 Pages: 76-80
  • Peer Reviewed
• [Journal Article] Spectroscopic and Theoretical Study of Endohedral Dimetallofullerene Having a Non-IPR Fullerene Cage : Ce_2@C_<72> (2008)
  • Author(s): M. Yamada, T. Wakahara, T. Tsuchiya, Y. Maeda, T. Akasaka, N. Mizorogi, S. Nagase
  • Journal Title: J. Phys. Chem. A 112 Pages: 7627-7631
  • Peer Reviewed
• [Journal Article] Isolation and Characterization of Carbene Derivatives of La@C_<82>(C_s) (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. A 112 Pages: 1294-1297
  • Peer Reviewed
• [Journal Article] Simple Purification and Selective Enrichment of Metallic SWCNTs Produced Using the Arc-discharge Method (2008)
  • Author(s): Y. Maeda, Y. Takano, A. Sagara, M. Hashimoto, M. Kanda, S. Kimura, Y. Lian, T. Nakahodo, T. Tsuchiya, T. Wakahara, T. Akasaka, T. Hasegawa, S. Kazaoui, N. Minami, J. Lu, S. Nagase
  • Journal Title: Carbon 46 Pages: 1563-156
  • Peer Reviewed
• [Journal Article] Preparation of Transparent and Conductive Thin Films of Metallic Single-walled Carbon Nanotubes (2008)
  • Author(s): Y. Maeda, M. Hashimoto, S. Kaneko, M. Kanda, T. Hasegawa, T. Tsuchiya, T. Akasaka, Y. Naitoh, T. Shimizu, H. Tokumoto, J. Lu, S. Nagase
  • Journal Title: J. Mater. Chem. 18 Pages: 4189-4192
  • Peer Reviewed
• [Journal Article] Synthesis of Selenylfullerene with Selenium-containing Dibenzo[b, g]cyclooctane Moiety (2008)
  • Author(s): T. Nakahodo, K. Takahashi, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, H. Fujihara, S. Nagase, T. Akasaka
  • Journal Title: Tetrahedron Lett. 49 Pages: 2302-2305
  • 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, K. Nakajima, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, M. T. H. Liu, N. Mizorogi, S. Nagase
  • Journal Title: Angew. Chem., Int. Ed. 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, M. Yamada, S. Takahashi, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, M. Kako, K. Yoza, E. Horn, N. Mizorogi, S. Nagase
  • Journal Title: Chem. Commun. Pages: 2680-2682
  • Peer Reviewed
• [Journal Article] Photo-labeling of C_<60> with 3-Trifluoromethyl-3-phenyldiazirine (2007)
  • Author(s): S. Sato, M. Yamada, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, T. Akasakaa, M. T. H. Liu,
  • 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. Ishituka, H. Enoki, H. Nikawa, T. Wakahara, T. Tsuchiya, T. Akasaka, M. T. H. Liu
  • Journal Title: Tetrahedron Lett. 48 Pages: 859-861
  • Peer Reviewed
• [Presentation] Construction of Supramolecular System Based on Endohedral Metallofullerene (2008)
  • Author(s): T. Tsuchiya, K. Sato, H. Kurihara, Y. Yokosawa, T. Akasaka, K. Ohkubo, S. Fukuzumi, T. Kato, S. Nagase
  • Organizer: PRiME (Pacific Rim Meeting) 2008
  • Place of Presentation: Honolulu, USA
  • Year and Date: 20081000
• [Presentation] 金属内包フラーレンに基づく超分子系の構築 (2008)
  • Author(s): 土屋 敬広
  • Organizer: 第40回構造有機化学若手の会夏の学校
  • Place of Presentation: 足和田ホテル
  • Year and Date: 20080806-08
• [Presentation] 金属内包フラーレンに基づく超分子系の構築 (2008)
  • Author(s): 土屋 敬広・佐藤 久美子・横澤 裕也・佐久間 理子・赤阪 健・加藤 立久・大久保 敬・福住 俊一・永瀬 茂
  • Organizer: 第3回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 上智大学
  • Year and Date: 20080531-0601
• [Presentation] Construction of Supramolecular System Based on Endohedral Metallofullerene (2008)
  • Author(s): T. Tsuchiya, K. Sato, H. Kurihara, N. Sakuma, T. Akasaka, K. Ohkubo, S. Fukuzumi, T. Kato, S. Nagase
  • Organizer: 213th Electro Chemical Society Meeting
  • Place of Presentation: Phoenix, USA
  • Year and Date: 20080500
• [Presentation] 金属内包フラーレンに基づく機能性センサーの構築 (2008)
  • Author(s): 土屋 敬広・赤阪 健
  • Organizer: TXテクノロジー・ショーケース・イン・ツクバ 2008
  • Place of Presentation: 産総研
  • Year and Date: 20080100
• [Presentation] 金属内包フラーレン配位子の合成と性質 (2008)
  • Author(s): 土屋 敬広・横澤裕也・赤阪 健
  • Organizer: 第2回有機π電子系シンポジウム
  • Place of Presentation: 宮島グランドホテル有もと
  • Year and Date: 2008-12-05
• [Presentation] 常磁性金属内包フラーレンに基づく超分子系の構築 (2008)
  • Author(s): 土屋 敬広
  • Organizer: 物性科学領域横断研究会 スピンが拓く物性科学の最前線
  • Place of Presentation: 東京大学
  • Year and Date: 2008-11-30
• [Presentation] 常磁性金属内包フラーレンに基づく超分子系の構築 (2008)
  • Author(s): 土屋 敬広・赤阪 健・大久保 敬・福住俊一・加藤立久・永瀬 茂
  • Organizer: 第19回日本化学会関東支部茨城地区研究交流会、
  • Place of Presentation: ワークプラザ勝田
  • Year and Date: 2008-11-21
• [Presentation] 金属内包フラーレン配位子の合成と性質 (2008)
  • Author(s): 土屋 敬広
  • Organizer: 第4回分子情報ダイナミクス研究会
  • Place of Presentation: 大阪大学
  • Year and Date: 2008-09-09
• [Presentation] 金属内包フラーレンを鍵物質とする超分子系の構築 (2007)
  • Author(s): 土屋 敬広・佐藤 久美子・佐久間 理子・栗原 広樹・赤阪 健・加藤 立久・大久保 敬・福住 俊一・溝呂木 直美・永瀬 茂
  • Organizer: 第34回有機典型元素化学討論会
  • Place of Presentation: 大阪大学
  • Year and Date: 20071200
• [Presentation] 金属内包フラーレンと有機ドナー分子に基づく可逆電子移動系の構築 (2007)
  • Author(s): 土屋 敬広・佐藤 久美子・赤阪 健・加藤 立久・大久保 敬・福住 俊一・永瀬 茂
  • Organizer: 第1回有機π電子系シンポジウム
  • Place of Presentation: 秋葉原ダイビル
  • Year and Date: 20071200
• [Presentation] 金属内包フラーレンと有機ドナー分子に基づく可逆電子移動系の構築 (2007)
  • Author(s): 土屋 敬広・佐久間 理子・佐藤 久美子・赤阪 健・加藤 立久・大久保 敬・福住 俊一・永瀬 茂
  • Organizer: 第37回構造有機化学討論会
  • Place of Presentation: 北海道大学
  • Year and Date: 20071000
• [Presentation] 常磁性金属内包フラーレンに基づく超分子系の構築 (2007)
  • Author(s): 土屋 敬広・佐藤 久美子・赤阪 健・加藤 立久・大久保 敬・福住 俊一・永瀬 茂
  • Organizer: 日本化学会第1回関東支部大会
  • Place of Presentation: 首都大学東京
  • Year and Date: 20070900
• [Presentation] 金属内包フラーレンと有機ドナー分子に基づく可逆電子移動系の構築 (2007)
  • Author(s): 土屋 敬広・佐久間 理子・佐藤 久美子・赤阪 健・加藤 立久・大久保 敬・福住 俊一・永瀬 茂
  • Organizer: 第3回分子情報ダイナミクス研究会
  • Place of Presentation: ホテル阪急エキスポパーク
  • Year and Date: 20070800
• [Presentation] Spin-Site Exchange System Constructed from Endohedral Metallofullerene and Organic Donor (2007)
  • Author(s): T. Tsuchiya, K. Sato, T. Wakahara, Y. Maeda, T. Akasaka, K. Ohkubo, S. Fukuzumi, T. Kato, S. Nagase
  • Organizer: 12th International Symposium on Novel Aromatic Compounds (ISNA-12)
  • Place of Presentation: Awaji, Japan
  • Year and Date: 20070700
• [Presentation] Spin-Site Exchange System Constructed from Endohedral Metallofullerene and Organic Donor (2007)
  • Author(s): T. Tsuchiya, K. Sato, T. Wakahara, Y. Maeda, T. Akasaka, K. Ohkubo, S. Fukuzumi, T. Kato, S. Nagase
  • Organizer: NIMS Conference 2007 on Recent Breakthroughs in Materials Science and Technology
  • Place of Presentation: Tsukuba, Japan
  • Year and Date: 20070700
• [Presentation] 金属内包フラーレンと有機ドナー分子に基づく可逆電子移動系の構築 (2007)
  • Author(s): 土屋 敬広・佐久間 理子・佐藤 久美子・若原 孝次・赤阪 健・加藤 立久・大久保 敬・福住 俊一・溝呂木 直美・永瀬 茂
  • Organizer: 第2回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 大阪市立大学
  • Year and Date: 20070500
• [Book] 新規フラーレン、カーボンナノチューブ系機能性材料の基礎研究, 51巻pp. 20-25 (2009)
  • Author(s): 土屋敬広 他
  • Publisher: 触媒学会誌
• [Remarks] ホームページ等
  • URL: http://www.tara.tsukuba.ac.jp/~akasaka-lab/
• [Remarks]
  • URL: http://www.nikkei-science.com/topics/bn0709_1.html