Studies on the responses to low magnetic and electric fields of chiral organic radical liquid crystals showing a ferromagnetic behavior at high temperatures

2010 Fiscal Year Final Research Report

• Project/Area Number: 19350067
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Kyoto University
• Principal Investigator: TAMURA Rui Kyoto University, 大学院・人間・環境学研究科, 教授 (60207256)
• Co-Investigator(Kenkyū-buntansha): TSUE Hirojhito 京都大学, 大学院・人間・環境学研究科, 准教授 (30271711) ; TAKAHASHI Hiroki 京都大学, 大学院・人間・環境学研究科, 助教 (00321779) ; SAKAI Naoko 京都大学, 大学院・人間・環境学研究科, 技術職員 (70447944)
• Project Period (FY): 2007 – 2010
• Keywords: ラジカル液晶 / 強誘電性液晶 / 常磁性液晶 / 強磁性的相互作用 / 磁場配向 / キラル液晶 / 光学活性液晶

Research Abstract

分子の中心部にニトロキシド構造を有する安定な中性およびイオン性のキラルモノラジカル液晶性化合物を種々合成することに成功した。ついで、これらの化合物の液晶相に弱い磁場を印加すると、スピングラスに類似の強い磁気相互作用(J > 0)が発現することを発見した。そこで、高温測定に有利な電子スピン共鳴スペクトル法を用いて、有機ラジカル液晶中で発現する磁気相互作用と分子・液晶相構造との相関関係を明らかにし、磁性発現のメカニズムを提唱した。

Research Products

• [Journal Article] Anisotropic and Inhomogeneous Magnetic Interactions Observed in All-Organic Nitroxide Radical Liquid Crystals. (2010)
  • Author(s): Uchida, Y., Suzuki, K., Tamura, R., Ikuma, N., Shimono, S., Noda, Y., Yamauchi, J.
  • Journal Title: Journal of The American Chemical Society 132 Pages: 9746-9752
  • Peer Reviewed
• [Journal Article] Second Harmonic Generation in a Paramagnetic All-Organic Chiral Smectic Liquid Crystal. (2010)
  • Author(s): Kogo, R., Araoka, F., Uchida, Y., Tamura R., Ishikawa, K., Takezoe, H
  • Journal Title: Applied Physics Express 3 Pages: 041701
  • Peer Reviewed
• [Journal Article] Preparation and Ferroelectric Properties of New Chiral Liquid Crystalline Organic Radical Compounds. (2010)
  • Author(s): Ikuma, N., Suzuki, K., Uchida, Y., Tamura R., Aoki, Y, Nohira, H.
  • Journal Title: Heterocycles 80 Pages: 527-535
  • Peer Reviewed
• [Journal Article] Chiral Symmetry Breaking Phenomenon Caused by a Phase Transition. (2010)
  • Author(s): Tamura, R., Iwama, S., Takahashi, H.
  • Journal Title: Symmetry(Review) 2 Pages: 112-135
  • Peer Reviewed
• [Journal Article] Observation of the Preferential Enrichment Phenomenon for Essential alpha-Amino Acids with a Racemic Crystal Structure. (2010)
  • Author(s): Iwama, S., Horiguchi, M., Sato, H., Uchida, Y., Takahashi, H., Tsue, H., Tamura, R.
  • Journal Title: Crystal Growth & Design 10 Pages: 2668-2675
  • Peer Reviewed
• [Journal Article] Magnetic-Field-Induced Molecular Alignment in the Achiral Liquid Crystal Spin-Labeled by a Nitroxyl Group in the Mesogen Core. (2009)
  • Author(s): Uchida, Y., Tamura, R., Ikuma, N., Shimono, S., Yamauchi, J., Shimbo, Y., Takezoe, H., Aoki, Y, Nohira, H.
  • Journal Title: Journal of Materials Chemistry 19 Pages: 415-418
  • Peer Reviewed
• [Journal Article] Electric, Electrochemical and Magnetic Properties of Novel Ionic Liquid Nitroxides, and Their Use as an EPR Spin Probe. (2009)
  • Author(s): Uchida, Y., Oki, S., Tamura, R., Sakaguchi, T., Suzuki, K., Ishibashi, K., Yamauchi, J.
  • Journal Title: Journal of Materials Chemistry 19 Pages: 6877-6881
  • Peer Reviewed
• [Journal Article] Preparation and Properties of C2-Symmetric Organic Radical Compounds Showing Ferroelectric Liquid Crystal Properties (2009)
  • Author(s): Ikuma, N., Uchida, Y., Tamura, R., Suzuki, K., Yamauchi, J., Aoki, Y, Nohira, H.
  • Journal Title: Molecular Crystals and Liquid Crystals 509 Pages: 108-117
  • Peer Reviewed
• [Journal Article] Grigor'ev, I. A., Synthesis and Stereochemistry of Novel Rigid Nitroxide Biradicals Based on Paramagnetic Pyrrolidine Core. (2009)
  • Author(s): Suzuki, K., Mazhukin, D. G., Takahashi, H., Uchida, Y., Tamura, R.
  • Journal Title: Heterocycles 78 Pages: 3091-3099
  • Peer Reviewed
• [Journal Article] Magnetic Characteristics and Orientation of a New Nitroxide Radical in an Ordered Matrix. (2008)
  • Author(s): Chumakova, N. A., Vorobiev, A. Kh., Ikuma, N., Uchida, Y., Tamura, R.
  • Journal Title: Mendeleev Communications 18 Pages: 221-223
  • Peer Reviewed
• [Journal Article] Partial Resolution of Racemic trans-4-[5-(4-Alkoxyphenyl)- 2,5-dimethylpyrrolidine-1-oxyl-2-yl] benzoic Acids by the Diastereomer Method with (R)- or (S)-1-Phenylethylamine. (2008)
  • Author(s): Uchida, Y., Uematsu, T., Nakayama, Y., Takahashi, H., Tsue, H., Tanaka, K., Tamura, R.
  • Journal Title: Chirality 20 Pages: 282-287
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Novel Radical Liquid Crystals Showing Ferroelectricity. (2008)
  • Author(s): Uchida, Y., Tamura, R., Ikuma, N., Yamauchi, J., Aoki, Y., Nohira, H.
  • Journal Title: Ferroelectrics 365 Pages: 158-169
  • Peer Reviewed
• [Journal Article] Unusual Intermolecular Magnetic Interaction Observed in an All-Organic Radical Liquid Crystal. (2008)
  • Author(s): Uchida, Y., Ikuma, N., Tamura, R., Shimono, S., Noda, Y., Yamauchi J., Aoki, Y, Nohira, H.,
  • Journal Title: Journal of Materials Chemistry 18 Pages: 2950-2952
  • Peer Reviewed
• [Journal Article] Paramagnetic All-Organic Chiral Liquid Crystals. (2008)
  • Author(s): Tamura, R., Uchida, Y., Ikuma, N.
  • Journal Title: Journal of Materials Chemistry(Highlight) 18 Pages: 2872-2876
  • Peer Reviewed
• [Journal Article] Enantiomeric Resolution of Racemic C2-Symmetric trans-2,5- Dimethyl-2,5-diphenylpyrrolidine and trans-2,5-Dimethyl-2,5-bis(3-hydroxy phenyl)pyrrolidine by a Diastereomer Method. (2008)
  • Author(s): Uchida, Y., Nakayama, Y., Suzuki, K., Oki, S., Horiguchi, M., Tsue, H., Tamura, R
  • Journal Title: Heterocycles 76 Pages: 875-881
  • Peer Reviewed
• [Journal Article] EPR Study of the Single Crystal of PROXYLs. (2008)
  • Author(s): Noda, Y., Shimono, S., Baba, M., Yamauchi, J., Uchida, Y., Ikuma, N., Tamura, R.
  • Journal Title: Applied Magnetic Resonances 33 Pages: 85-93
  • Peer Reviewed
• [Journal Article] Origin of the Difference in Phase Transition Behavior between Two Type of All-Organic Radical Liquid Crystals. (2008)
  • Author(s): Uchida, Y., Tamura, R., Ikuma, N., Shimono, S., Takahashi, H., Yamauchi, J
  • Journal Title: Advances in Science and Technology 55 Pages: 42-45
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Novel All-Organic Liquid Crystalline Radicals. (2007)
  • Author(s): Uchida, Y., Tamura, R., Ikuma, N., Shimono, S., Yamauchi, J., Aoki, Y., Nohira, H.
  • Journal Title: Molecular Crystals and Liquid Crystals 479 Pages: 213-221
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure, and Magnetic Properties of 4-(2-Methyl-1-azaspiro[4.5]deca-1-oxyl-2-yl)phenol. (2007)
  • Author(s): Uchida, Y., Matsuoka, N., Takahashi, T., Shimono, S., Ikuma, N., Tamura, R.
  • Journal Title: Heterocycles 74 Pages: 607-616
  • Peer Reviewed
• [Journal Article] Mechanistic Flexibility of Solvent-Assisted Solid-to-Solid Polymorphic Transition Causing Preferential Enrichment : Significant Contribution of ?/? and CH/??Interactions as Well as Hydrogen Bonds. (2007)
  • Author(s): Horiguchi, M., Okuhara, S., Shimano, E., Fujimoto, D., Takahashi, H., Tsue, H., Tamura, R.
  • Journal Title: Crystal Growth & Design 7 Pages: 1643-1652
  • Peer Reviewed
• [Presentation] 優先富化現象を用いたキラルサイエンス (2011)
  • Author(s): 田村類
  • Organizer: 2nd Symposium on Chiral Science & Technology: Mesochemistry & Chemical Wisdom
  • Place of Presentation: 東京
  • Year and Date: 2011-03-02
• [Presentation] Recent Advances in Preparatioon and Magnetic Properties of All-Organic Chiral Nitroxide Radical Liquid Crystals (2010)
  • Author(s): 田村類, et al.
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA.
  • Year and Date: 2010-12-18
• [Presentation] Preferential Enrichment of Amino Acid-Organic Acid Cocrystals with a Racemic Crystal Structure. (2010)
  • Author(s): 田村類, et al.
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA.
  • Year and Date: 2010-12-15
• [Presentation] Preferential Enrichment of Amino Acids with a Racemic Crystal Structure. (2010)
  • Author(s): 田村類, et al.
  • Organizer: 9th International Workshop on Crystal Growth of Organic Materials
  • Place of Presentation: Singapore
  • Year and Date: 2010-08-07
• [Presentation] Preferential Enrichment Phenomenon of Amino Acids with Racemic Crystal Structure. (2010)
  • Author(s): 田村類, et al.
  • Organizer: 22nd International Symposium on Chirality
  • Place of Presentation: Sapporo, Japan.
  • Year and Date: 2010-07-14
• [Presentation] Ferroelectric and Unusual Magnetic Properties of All-Organic Chiral Nitroxide Radical Liquid Crystals. (2009)
  • Author(s): 田村類, et al.
  • Organizer: 3rd Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
  • Place of Presentation: Awaji Island, Japan.
  • Year and Date: 2009-11-18
• [Presentation] Ferroelectric and Ferromagnetic Properties of All-Organic Chiral Nitroxide Radical Liquid Crystals. (2009)
  • Author(s): 田村類, et al.
  • Organizer: 19th International Conference on the Chemistry of Organic Solid State
  • Place of Presentation: Sestri Levante, Italy.
  • Year and Date: 2009-06-18
• [Presentation] Paramagnetic All-Organic Chiral Liquid Crystals as Soft Magnetic Materials. (2009)
  • Author(s): 田村類, et al.
  • Organizer: 4th East Asia Symposium on Functional Dyes and Advanced Materials
  • Place of Presentation: Osaka, Japan.
  • Year and Date: 2009-06-03
• [Presentation] Ferroelectric and Ferromagnetic Properties of All-Organic Nitroxide Radical Liquid Crystals. (2008)
  • Author(s): 田村類, et al.
  • Organizer: The IUMRS International Conference in Asia
  • Place of Presentation: Nagoya, Japan.
  • Year and Date: 2008-12-12
• [Presentation] 有機ラジカル液晶の強磁性と強誘電性および磁気電気相互作用. (2008)
  • Author(s): 田村類
  • Organizer: 日本液晶学会主催 「液晶物理・物性」 「液晶化学・材料」 「ソフトマター」研究フォーラム合同講演会『周期構造と機能』
  • Place of Presentation: 三浦市
  • Year and Date: 2008-11-21
• [Presentation] Ferromagnetic and Ferroelectric Properties of Paramagnetic All-Organic Liquid Crystals Containing a Chiral Cyclic-Nitroxide Unit. (2008)
  • Author(s): 田村類, et al.
  • Organizer: 5th International Conference on Nitroxide Radical (SPIN 2008)
  • Place of Presentation: Ancona, Italy
  • Year and Date: 2008-09-11
• [Presentation] キラル分子間の分子認識:優先富化現象の分子メカニズム (2008)
  • Author(s): 田村類
  • Organizer: 第298情報計算化学生物(CBI)学会研究講演会(『低分子X 線解析から分かること:構造解析から分子設計へ』)
  • Place of Presentation: 東京
  • Year and Date: 2008-07-21
• [Presentation] Ferroelectric and Mesoscopical-Magnetic Properties of All-Organic Chiral Nitroxide Radical Liquid Crystals. (2008)
  • Author(s): 田村類
  • Organizer: 3rd International Conference on Smart Materials, Structures and Systems (CIMTEC)
  • Place of Presentation: Acireale, Italy.
  • Year and Date: 2008-06-10
• [Presentation] 相転移による対称性の破れに起因する2つの複雑系化学現象?優先富化現象と有機ラジカル液晶の強磁性的挙動. (2007)
  • Author(s): 田村類
  • Organizer: 日本プロセス学会2007 サマーシンポジウム
  • Place of Presentation: 東京
  • Year and Date: 20070800
• [Presentation] Control of Polymorphic Transition Inducing Preferential Enrichment by Modifying Molecular Structures or Adding Seed Crystals. (2007)
  • Author(s): 田村類
  • Organizer: 8th Conference of the Asian Crystallographic Association
  • Place of Presentation: Taipei, Taiwan.
  • Year and Date: 2007-11-05
• [Presentation] Chiral Separation via Preferential Enrichment. (2007)
  • Author(s): 田村類
  • Organizer: 15th Larson Workshop
  • Place of Presentation: Madison, USA.
  • Year and Date: 2007-10-09
• [Presentation] Ferroelectric and Magnetic Properties of All-Organic Radical Liquid Crystals (2007)
  • Author(s): 田村類, et al.
  • Organizer: 11th Ferroelectric Liquid Crystal Conference
  • Place of Presentation: Sapporo, Japan.
  • Year and Date: 2007-09-03
• [Presentation] Synthesis and Ferroelectric and Ferromagnetic Properties of All-Organic Liquid Crystalline Radicals. (2007)
  • Author(s): 田村類, et al.
  • Organizer: Post-Symposium of ISNA in Himeji/Harima on Functional Aromatic Compounds,
  • Place of Presentation: Hyogo, Japan.
  • Year and Date: 2007-07-30
• [Book] キラル有機ラジカル液晶の合成と磁気電気物性, (液晶-構造制御と機能化の最前線-)(加藤隆史監修) (2010)
  • Author(s): 田村類, 内田幸明, 鈴木克明
  • Total Pages: 179-192
  • Publisher: シーエムシー出版
• [Book] California, American Scientific Publishers (2009)
  • Author(s): Rui Tamura, Naohiko Ikuma, Satoshi Shimono, Soft Nanomaterials, H.S.Nalwa (ed.)
  • Total Pages: 257-277
• [Book] Application in Chemistry, Biochemistry, and Materials Science (2008)
  • Author(s): Rui Tamura, Nitroxide
  • Total Pages: 303-329
  • Publisher: Wiley-VCH
• [Remarks] ホームページ等
  • URL: http://www.users.iimc.kyoto-u.ac.jp/~z59081/
• [Patent(Industrial Property Rights)] 新規有機常磁性イオン液体化合物及びそれを含む支持電解質 (2008)
  • Inventor(s): 田村類・内田幸明・沖成昭・酒井健一
  • Industrial Property Rights Holder: 東レ・ファインケミカル(株)
  • Industrial Property Number: 特許,特許公開2009-215182
  • Filing Date: 2008-03-07
• [Patent(Industrial Property Rights)] 新規液晶化合物及びその分子集合体の移動を制御する方法 (2008)
  • Inventor(s): 田村類・内田幸明・鈴木克明・酒井健一
  • Industrial Property Rights Holder: 東レ・ファインケミカル(株)
  • Industrial Property Number: 特許,特許公開2009-215187
  • Filing Date: 2008-03-07
• [Patent(Industrial Property Rights)] 分子集合体の移動を制御する方法 (2007)
  • Inventor(s): 田村類・内田幸明・伊熊直彦
  • Industrial Property Rights Holder: 東レ・ファインケミカル(株)
  • Industrial Property Number: 特許,特許公開2009-079020
  • Filing Date: 2007-09-27