超分子構造を包含する元素ブロック高分子の階層化と機能開拓

• Project Area: Creation of Element-Block Polymer Materials
• Project/Area Number: 15H00717
• 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): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2016: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2015: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 強誘電性 / 磁性 / マルチフェロイック / 超分子 / キラル磁性

Outline of Annual Research Achievements

金属錯体をアニオンと、カチオン性超分子ローター構造からなる階層構造を構築し、結晶内での分子運動と、金属錯体に基づく磁性を基盤とした新奇機能性の開拓目指し研究を進めている。本研究においては、結晶内での階層構造を制御する手段として、分子間相互作用に加えて分子の対称性に注目し、結晶の対称性に基づく分子配列制御を試みた。結晶内における分子運動を制御するためには、最密充填した結晶内での空間を確保することが必須であり、構成成分である超分子構造の配列制御不可欠となる。また、２次元強磁性”元素ブロック高分子”と分子ローター型超分子強誘電体の複合化を行った。特に、キラルな超分子構造により、二次元強磁性”元素ブロック高分子”にキラリティを誘起し、キラル磁性に基づく光磁気機能性の開拓を目指した。
C2h点群に属する平面的な構造をとるtst-DCH[18]crown-6 (tst-DCH = trans-syn-trans-dicyclohexano)が結晶内で反転対称中心になり、その結果、分子の上下に同一の環境を与えることを利用して、結晶内でのカラム構造やプロトン移動可能な超分子構造を構築できることを明らかにし、元素ブロック高分子のユニットとしての有用性を示した。また、2次元強磁性金属錯体ユニットにキラリティを誘起する目的で、(R)-α-aminoethanolのプロトン化体 (RHPA+)を用いて、(RHPA+)(cis-syn-cis-DCH[18]crown-6)[MnCr(oxalate)3]-(CH3CN)結晶を作製した。結晶の空間群はP1であり、Flack parameterはほぼ0であるキラルな結晶を得ることができ、錯体部分のキラリティが誘起されていることを確認し、キラル磁性体探索のための有望な物質群となり得ることを示した。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Temperature-Dependent Mechanochromic Behavior of Mechanoresponsive Luminescent Compounds (2017)
  • Author(s): Y. Sagara, K. Kubo, T. Nakamura, N. Tamaoki and C. Weder
  • Journal Title: Chemistry of Materials Volume: 29 Issue: 3 Pages: 1273-1278
  • DOI: 10.1021/acs.chemmater.6b04720
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Successive Phase Transition, Dielectric Ordering, and Liquid Crystalline Behavior of Simple (Laurylammonium)(Phenyl Phosphates) Salts (2016)
  • Author(s): Z. S. Cai, S. Uchikawa, N. Hoshino, T. Takeda, L. M. Zheng, S. Noro, T. Nakamura and T. Akutagawa
  • Journal Title: J. Phys. Chem. B Volume: 120 Issue: 27 Pages: 6761-6770
  • DOI: 10.1021/acs.jpcb.6b02213
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Poly(4-styrenesulfonate) Templated Polyaniline-Carboxymethyl Cellulose Blend: Morphology and Surface Resistivity of the Spin-Coated Films (2016)
  • Author(s): T. Nakamura and S. Jayanty
  • Journal Title: Soft Materials Volume: 14 Issue: 4 Pages: 309-315
  • DOI: 10.1080/1539445x.2016.1215330
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] One-dimensional Supramolecular Columnar Structure of trans-syn-trans-dicyclohexano[18]crown-6 and Organic Ammonium Cations (2016)
  • Author(s): Y. Ohshima, K. Kubo, T. Matsumoto, H. Y. Ye, S. Noro, T. Akutagawa and T. Nakamura
  • Journal Title: CrystEngComn Volume: 18 Issue: 41 Pages: 7959-7964
  • DOI: 10.1039/c6ce00980h
  • NAID: 120005859711
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] A Highly Water-Tolerant Magnesium(II) Coordination Polymer Derived from a Flexible Layered Structure (2016)
  • Author(s): R. Ochi, S. Noro, Y. Kamiya, K. Kubo and T. Nakamura
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 31 Pages: 11042-11047
  • DOI: 10.1002/chem.201600843
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] The crystal design of polar one-dimensional hydrogen-bonded copper coordination complexes (2016)
  • Author(s): Takahashi, K.; Hoshino, N.; Takeda, T.; Satomi, K.; Suzuki, Y.; Noro, S.; Nakamura, T.; Kawamata, J.; Akutagawa, T.
  • Journal Title: Dalton Transactions Volume: 45 Issue: 8 Pages: 3398-3406
  • DOI: 10.1039/c5dt04865f
  • Peer Reviewed
• [Journal Article] Self-assembled Structure of Inorganic/Organic Hybrid Crystals Based on Keggin Polyoxometallates [SMo12O402-] and Supramolecular Cations (2016)
  • Author(s): Jun Xiong, Kazuya Kubo, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Crystal Growth & Design Volume: 16 Issue: 2 Pages: 800-807
  • DOI: 10.1021/acs.cgd.5b01388
  • Peer Reviewed
• [Journal Article] Structural Design of Coordination Polymers Based on Manganese and Chromium Ions Bridged by Oxalate Ligands (2016)
  • Author(s): Masashi Yoshitake, Kazuya Kubo, Toru Endo, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 89 Issue: 3 Pages: 354-360
  • DOI: 10.1246/bcsj.20150373
  • NAID: 130005137575
  • ISSN: 0009-2673, 1348-0634
  • Peer Reviewed / Open Access
• [Journal Article] Structural Flexibilities and Gas Adsorption Properties of One-Dimensional Copper(II) Polymers with Paddle-Wheel Units by Modification of Benzoate Ligands (2015)
  • Author(s): Takahashi, K.; Hoshino, N.; Takeda, T.; Noro, S.; Nakamura, T.; Takeda, S.; Akutagawa, T.
  • Journal Title: Inorganic Chemistry Volume: 54 Issue: 19 Pages: 9423-9423
  • DOI: 10.1021/acs.inorgchem.5b01168
  • Peer Reviewed
• [Journal Article] High CO2/CH4 Selectivity of a Flexible Copper(II) Porous Coordination Polymer under Humid Conditions (2015)
  • Author(s): S. Noro, R. Matsuda, Y. Hijikata, Y. Inubushi, S. Takeda, S. Kitagawa, Y. Takahashi, M. Yoshitake, K. Kubo and T. Nakamura,
  • Journal Title: ChemPlusChem. Volume: 80 Issue: 10 Pages: 1517-1524
  • DOI: 10.1002/cplu.201500278
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Liquid Crystalline Phase Induced by Molecular Rotator and Dipole Fluctuation (2015)
  • Author(s): Zhang, Q.-C.; Takeda, T.; Hoshino, N.; Noro, S.; Nakamura, T.; Akutagawa, T.
  • Journal Title: Crystal Growth & Design Volume: 15 Issue: 12 Pages: 5705-5711
  • DOI: 10.1021/acs.cgd.5b00695
  • Peer Reviewed
• [Journal Article] Crystal-to-crystal structural transformation of hydrogen-bonding molecular crystals of (imidazolium)(3-hydroxy-2-quinoxalinecarboxylate) through H2O adsorption-desorption (2015)
  • Author(s): Yoshii, Y.; Sakai, K.; Hoshino, N.; Takeda, T.; Noro, S.; Nakamura, T.; Akutagawa, T.
  • Journal Title: CrystEngComm Volume: 17 Issue: 31 Pages: 5962-5969
  • DOI: 10.1039/c4ce02519a
  • Peer Reviewed
• [Presentation] Functional Magnetic Materials based on Mn-Cr Oxalate Complexes with Supramolecular Rotator Structure (2016)
  • Author(s): T. Nakamura, M. Yoshitake, K. Kubo and S. Noro
  • Organizer: The 8th International Symposium on Nano & Supramolecular Chemistry
  • Place of Presentation: Brisbane, Australia
  • Year and Date: 2016-07-13
  • Int'l Joint Research / Invited
• [Presentation] Functional Materials based on Ferromagnetic Coordination Polymer of Mn-Cr Oxalate (2015)
  • Author(s): T. Nakamura
  • Organizer: Pacific Polymer Conference 14
  • Place of Presentation: Kauai, Hawaii, USA
  • Year and Date: 2015-12-09
  • Int'l Joint Research / Invited
• [Presentation] 分子回転を利用した強誘電性分子性材料の開拓 (2015)
  • Author(s): 中村 貴義、久保 和也、野呂 真一郎、芥川 智行
  • Organizer: 電気情報通信学会 有機エレクトロニクス研究会(OME)
  • Place of Presentation: 東京都港区機械振興会館
  • Year and Date: 2015-11-06
  • Invited
• [Presentation] Molecular and ionic motions in the solid state (2015)
  • Author(s): T. Nakamura
  • Organizer: Core-to-Core/Leverhulme Trust Joint Workshop, Moscow 2015 “Organic Electronics of Highly-Correlated Molecular Systems”
  • Place of Presentation: Moscow, Russia
  • Year and Date: 2015-10-08
  • Int'l Joint Research / Invited