超分子ローター構造を包含する元素ブロック高分子の階層化と機能相関

• Project Area: Creation of Element-Block Polymer Materials
• Project/Area Number: 25102502
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 中村 貴義 北海道大学, 電子科学研究所, 教授 (60270790)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2013: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: 誘電性 / 磁性 / 超分子構造 / 分子ローター / ポリオキソメタレート

Outline of Annual Research Achievements

磁性を示す金属錯体を基本ユニットとするアニオンと、強誘電性を発現するカチオン性超分子ローター構造からなる元素ブロック階層構造を構築し、機能相関に基づく新奇機能性の開拓を行うことが、本研究の目的である。本年度は強磁性と強誘電性の共存を目指し、
強磁性アニオンと分子回転運動が可能な超分子カチオンを組み合わせた階層性元素ブロック高分子の開拓を行った。アニオンとして巨大分子であるポリオキソメタレート（POM）をとりあげ、水素結合等の弱い相互作用を通じて分子ローター構造との階層構造の形成を目指した。さらに、キラルな超分子を導入し、キラル磁性の発現を図るための予備実験を行った。
強磁性を発現する高分子錯体として[MnCr(oxalate)3]-アニオンを選択し、昨年度までに得られた、 (m-fluoroanilinium+)(trans-syn-trans-dicyclohexano[18]crown-6) [MnCr(oxalate)3]-について検討を行った。X結晶構造解析の結果、m-fluoro基にディスオーダーが見られた。また、DSCにより、250K付近に相転移の徴候が見られた。結晶が微小で、誘電率測定が困難であったため、SHGの温度変化測定を行ったところ、結晶の対称性低下に伴うと考えられるシグナルが観察された。現在、詳細な検討を進めている。
また、種々のPOMをカウンターアニオンとする結晶を作製し、結晶内における分子ローター構造を精査した。特に、結晶内の水素結合と結晶構造の相関について検討を行った。
さらに、[MnCr(oxalate)3]-アニオンのカウンターカチオンとしてキラルなアンモニウムを含む超分子を導入し、結晶を作製した。キラル磁性体の候補として、次年度以降の研究の端緒が得られた。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Supramolecular cations of (m-halogenated-anilinium)(dibenzo[18]crown-6) in Keggin [SMo12O402−] polyoxometallates (2015)
  • Author(s): J. Xiong, K. Kubo, S. Noro, T. Akutagawa, and N. Nakamura
  • Journal Title: CrystEngComm. Volume: 17 Issue: 4 Pages: 856-861
  • DOI: 10.1039/c4ce01988a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand (2015)
  • Author(s): Shin-ichiro Noro, Junya Mizutani, Yuh Hijikata, Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa, Kunihisa Sugimoto, Yasutaka Inubushi, Kazuya Kubo, and Takayoshi Nakamura
  • Journal Title: Nature Communications Volume: 6 Issue: 1 Pages: 5851-5851
  • DOI: 10.1038/ncomms6851
  • NAID: 120005745622
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Mesophases and Ionic Conductivities of Simple Organic Salts of M(m-Iodobenzoate) (M = Li+, Na+, K+, Rb+, and Cs+) (2015)
  • Author(s): Manami Endo, Yuta Nakane, Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Shin-ichiro Noro, Takayoshi Nakamura, and Tomoyuki Akutagawa
  • Journal Title: Journal of Physical Chemistry B Volume: 119 Issue: 4 Pages: 1768-1777
  • DOI: 10.1021/jp5112026
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Three-dimensional Architectures of [MnIICrIII(oxalate)3]; Complexes with Cage Type Networks Surrounding Supramolecular Cations (2015)
  • Author(s): Toru Endo, Kazuya Kubo, Masashi Yoshitake, Shin-ichiro Noro, Norihisa hoshino, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: rystal Growth & Design Volume: 15 Issue: 3 Pages: 1186-1193
  • DOI: 10.1021/cg501560z
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Electron-deficient Acene-based Liquid Crystals: Dialkoxydicyanopyrazinoquinoxalines (2015)
  • Author(s): Takashi Takeda, Jun’ya Tsutsumi, Tatsuo Hasegawa, Shin-ichiro Noro, Takayoshi Nakamura, and Tomoyuki Akutagawa
  • Journal Title: J. Mater. Chem. C. Volume: 3 Issue: 13 Pages: 3016-3022
  • DOI: 10.1039/c5tc00022j
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Gold nanoparticle assemblies stabilized by bis(phthalocyaninato)lanthanide(III) complexes through van der Waals interactions (2015)
  • Author(s): Yuki Noda, Shin-ichiro Noro, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Journal Title: Scientific Reports Volume: 4 Issue: 1 Pages: 3758-3758
  • DOI: 10.1038/srep03758
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Molecular Assembly and Ferroelectric Response of Benzenecarboxamides Bearing Multiple -CONHC14H29 Chains (2014)
  • Author(s): Yuta Shishido, Hayato Anetai, Takashi Takeda, Norihisa Hoshino, Shin-ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: J. Phys. Chem. C. Volume: 118 Issue: 36 Pages: 21204-21214
  • DOI: 10.1021/jp506035h
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Crystal Structure and Physical Properties of a Dithiolene Complex Crystal with Adamantane Supramolecular Rotator (2014)
  • Author(s): Yin-Nan Yan, Kazuya Kubo, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 87 Issue: 3 Pages: 417-419
  • DOI: 10.1246/bcsj.20130316
  • NAID: 130004153287
  • ISSN: 0009-2673, 1348-0634
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Crystal structures, CO2 adsorption, and dielectric properties of [Cu(II)2(R-benzoate)4(pyrazine)]∞ polymers (R = m-F, 2,3-F2, m-Cl, and m-CH3) (2014)
  • Author(s): Kiyonori Takahashi, Norihisa Hoshino, Takashi Takeda, Shin-ichiro Noro, Takayoshi Nakamura, Sadamu Takeda and Tomoyuki Akutagawa
  • Journal Title: Dalton Transactions Volume: 43 Issue: 24 Pages: 9081-9089
  • DOI: 10.1039/c4dt00258j
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Finite Winding (H₂O)₁₂ Chain Stabilized by One-Dimensional Coordination Polymer (2014)
  • Author(s): Shin-ichiro Noro, Kei Hasegawa, Kazuya Kubo, and Takayoshi Nakamura
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 87 Issue: 5 Pages: 623-625
  • DOI: 10.1246/bcsj.20140005
  • NAID: 130004153293
  • ISSN: 0009-2673, 1348-0634
  • Peer Reviewed
• [Journal Article] The Formation of Organogels and Helical Nanofibers from Simple Organic Salts (2014)
  • Author(s): Yuya Yoshii, Norihisa Hoshino, Takashi Takeda, Hiroki Moritomo, Jun Kawamata,Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: Chemistry - A European Journal Volume: 20 Issue: 49 Pages: 16279-16285
  • DOI: 10.1002/chem.201404043
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Design of Crystalline Spaces for Molecular Rotations in Crystals (2014)
  • Author(s): Z. Q. Liu, K. Kubo, S. Noro, T. Akutagawa and T. Nakamura
  • Journal Title: Crystal Growth & Design Volume: 14 Issue: 2 Pages: 537-543
  • DOI: 10.1021/cg4013262
  • Peer Reviewed
• [Journal Article] Dielectric and Structural Phase Transition of [Ni(dmit)2]- Salt with (4-ethoxyanilinium)([18]crown-6) Supramolecular Cation (2013)
  • Author(s): Q. Ye, P. P. Shi, X. Q. Fu, T. Akutagawa and T. Nakamura
  • Journal Title: CrystEngCommun Volume: 15 Issue: 26 Pages: 5307-5313
  • DOI: 10.1039/c3ce40220g
  • Peer Reviewed
• [Journal Article] Molecule-Displacive Ferroelectricity in Organic Supramolecular Solids (2013)
  • Author(s): H. Ye, Y. Zhang, S. Noro, K. Kubo, M. Yoshitake, Z. Liu, H. Cai, D. Fu, H. Yoshikawa, K. Awaga, R. G. Xiong and T. Nakamura
  • Journal Title: Scientific Reports Volume: 3 Issue: 1 Pages: 2249-2249
  • DOI: 10.1038/srep02249
  • NAID: 120006795651
  • Peer Reviewed
• [Journal Article] Porous Coordination Polymer Polymorphs with Different Flexible Pores Using a Structurally Flexible and Bent 1, 3-Bis(4-pyridyl)propane Ligand (2013)
  • Author(s): K. Fukuhara, S. Noro, K. Sugimoto, T. Akutagawa, K. Kubo and T. Nakamura
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 8 Pages: 4229-4237
  • DOI: 10.1021/ic301949n
  • Peer Reviewed
• [Journal Article] Rational Synthesis of a Porous Copper(II) Coordination Polymer Bridged by Weak Lewis-Base Inorganic Monoanions Using an Anion-Mixing Method (2013)
  • Author(s): S. Noro, K. Fukuhara, Y. Hijikata, K. Kubo and T. Nakamura
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 10 Pages: 5630-5635
  • DOI: 10.1021/ic400276c
  • Peer Reviewed
• [Journal Article] Graphene Oxide Nanosheet with High Proton Conductivity (2013)
  • Author(s): M. Karim, K. Hatakeyama. T. Matsui, H. Takehiro, T. Taniguchi, M. Koinuma, Y. Matsumoto, T. Autogawa, T. Nakamura, S. Noro, T. Yamada, H. kitagawa, S. Hayami
  • Journal Title: Journal of the American Chemical Society Volume: 135 Issue: 22 Pages: 8097-8100
  • DOI: 10.1021/ja401060q
  • URL: http://dx.doi.org/10.1021/ja401060q
  • Peer Reviewed
• [Journal Article] Magnetic Ordering of Spin Systems Having Fractal Dimensions Experimental Study (2013)
  • Author(s): T. Naito, H. Yamamoto, K. Okuda. K. Konishi, H. Mayama, D. Yamaguchi, S. Koizumi, K. Kubo, T. Nakamura, T. Yamada, H. Kitagawa, and S. Hayami
  • Journal Title: Eur. Phys. J. B Volume: 86 Issue: 10 Pages: 410-410
  • DOI: 10.1140/epjb/e2013-40353-3
  • Peer Reviewed
• [Journal Article] The effect of doping a molecular spin ladder with non-magnetic impurities (2013)
  • Author(s): S. Nishihara, X. Zhang, K. Kunishio, K. Inoue, XM. Ren, T. Akutagawa, J. Kishine, M. Fujisawa, A. Asakura, S. Okubo, H. Ohta, T. Nakamura
  • Journal Title: Dalton Transactions Volume: 42 Issue: 43 Pages: 15263-15266
  • DOI: 10.1039/c3dt52249k
  • Peer Reviewed
• [Journal Article] Anion-Dependent Host-Guest Properties of Porous Assemblies of Coordination Complexes (PACs), [Cu(A)2(py)4] (A = PF6, BF4, CF3SO3, and CH3SO3; py = pyridine), based on Werner-Type Copper(II) Complexes in the Solid State (2013)
  • Author(s): S. Noro, K. Fukuhara, K, Sugimoto, Y. Hijikata, K. Kubo and T. Nakamura
  • Journal Title: Dalton Trans Volume: 42 Issue: 31 Pages: 11100-11110
  • DOI: 10.1039/c3dt51104a
  • Peer Reviewed
• [Journal Article] Crystal Structure of a Supramolecular Cation Salt: (adamantylammonium+)2(benzo[18]crown-6)2[Pd(dmit)2]2-(acetone)2 (2013)
  • Author(s): Kazuya Kubo, Yin-Nan Yan, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Inorganica Chimica Acta Volume: 404 Pages: 206-209
  • DOI: 10.1016/j.ica.2013.02.018
  • Peer Reviewed
• [Presentation] Functional Magnetic Materials based on Mn-Cr Oxalte Complexs (2014)
  • Author(s): Nakamura, T
  • Organizer: 10th IUPAC International Conference on Novel Materials and their Synthesis (NMS-X)
  • Place of Presentation: Zengzhou, China
  • Year and Date: 2014-10-11 – 2014-10-15
  • Invited
• [Presentation] Structure and physical properties of ferromagnetic crystals with supramolecular cations (2014)
  • Author(s): Kubo, K.;, Endo, T.; Yoshitake, M.; Hoshino, N.;, Akutagawa, T.; Noro, S.; Nakamura, T.
  • Organizer: 3rd International Conference and Exhibition on Materials Science & Engineering
  • Place of Presentation: San Antonio, USA
  • Year and Date: 2014-10-06 – 2014-10-08
  • Invited
• [Presentation] Dielectrics based on Supramolecular Rotators (2014)
  • Author(s): Nakamura, T.
  • Organizer: The 8th International Symposium on Organic Molecular Electronics (ISOME 2014)
  • Place of Presentation: 東京農工大学（小金井市）
  • Year and Date: 2014-05-15 – 2014-05-16
  • Invited
• [Presentation] Dielectrics based on Supramolecular Rotator Units in Single Crystals (2014)
  • Author(s): T. Nakamura
  • Organizer: Symposium on Molecular Science and Synthesis of Functional Molecules for Next Generation
  • Place of Presentation: 広島大学 （広島県）
  • Invited
• [Presentation] 超分子構造を利用した誘電体結晶の開拓 (2014)
  • Author(s): 中村貴義
  • Organizer: 総合研究機構分子連関相乗系研究部門平成25年度成果報告会
  • Place of Presentation: 東京理科大学 （東京都）
  • Invited
• [Presentation] Supramolecular Rotators for Ferroelectrics and Multiferroics (2013)
  • Author(s): 28) T. Nakamura, S. Yoshitake, K. Kubo, S. Noro and T. Akutagawa
  • Organizer: The 15th Asian Chemical Congress
  • Place of Presentation: Resorts World Sentosa (Sentosa, Singapore）
  • Invited