Development of ferroelectrics based on molecular rotators

• Project/Area Number: 23350085
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials/Devices
• Research Institution: Hokkaido University
• Principal Investigator: NAKAMURA Takayoshi 北海道大学, 電子科学研究所, 教授 (60270790)
• Co-Investigator(Renkei-kenkyūsha): KUBO Kazuya 北海道大学, 電子科学研究所, 助教 (90391937)
• Project Period (FY): 2011-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥20,150,000 (Direct Cost: ¥15,500,000、Indirect Cost: ¥4,650,000); Fiscal Year 2013: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2012: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2011: ¥10,140,000 (Direct Cost: ¥7,800,000、Indirect Cost: ¥2,340,000)
• Keywords: 分子ローター / 強誘電性 / 超分子 / クラウンエーテル / 磁性 / 強誘電体

Research Abstract

Dielectric properties based on flip-flop motion of dipoles upon molecular rotation were investigated by changing arylammonium and crown ether derivatives. Adamantane derivative with pseudo C3 symmetry was also studied. Although pyridazinium has no NH3 substituent worked as rotational axis, the molecule can be fixed by weak hydrogen bonds in the crystalline voids. The molecular motion upon applying external field was resulted in a large dielectric response. It was also attempted to introduce two proton accepting sites in the rotator to evaluate the possibility of hybrid dielectric response by proton transfer and molecular rotation.

Research Products

• [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 Pages: 3758-3758
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  • Peer Reviewed / Open Access / 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 Pages: 537-543
  • DOI: 10.1021/cg4013262
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• [Journal Article] Molecular motion in pyridazinium/crown ether supramolecular cation salts of a nickel dithiolene complex (2013)
  • Author(s): Zun-qi Liu, Li Lin, Kazuya Kubo, Nirihisa Hoshino, Shin-ichiro Noro, Tomoyuki Akutagawa,* Takayoshi Nakamura
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• [Journal Article] Highly Selective CO2 Adsorption Accompanied with Low-Energy Regeneration in a Two-Dimensional Cu(II) Porous Coordination Polymer with Inorganic Fluorinated PF6- Anions (2013)
  • Author(s): S. Noro, T. Fukushima, S. Kitagawa, T. Nakamura, 他
  • Journal Title: Inorg. Chem. Volume: 52 Pages: 280-285
  • DOI: 10.1021/ic301823j
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• [Journal Article] (3-Fluoro-4-methoxyanilinium)⁺([18]Crown-6) Supramolecular Cation Salt of Ferromagnetic [Mn^IICr^III(oxalate)₃]^− (2013)
  • Author(s): Toru Endo, Kazuya Kubo, Masashi Yoshitake, Shin-ichiro Noro, Tomoyuki Akutagawa, and Takayoshi Nakamura
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  • DOI: 10.1246/cl.2013.137
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• [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
• [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 Pages: 5307-5313
  • DOI: 10.1039/c3ce40220g
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• [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: Sci. Rep. Volume: 3 Pages: 2249-2249
  • DOI: 10.1038/srep02249
  • 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 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 Pages: 5630-5632
  • DOI: 10.1021/ic400276c
  • Peer Reviewed
• [Journal Article] Anion-dependent host/guest properties of porous assemblies of co-ordination 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 Pages: 11100-11110
  • DOI: 10.1039/c3dt51104a
  • 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: J. Am. Chem. Soc Volume: 135 Pages: 8097-8100
  • DOI: 10.1021/ja401060q
  • URL: http://dx.doi.org/10.1021/ja401060q
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• [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: European Physical Journal B Volume: 86 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 Pages: 15263-15266
  • DOI: 10.1039/c3dt52249k
  • Peer Reviewed
• [Journal Article] Molecular Motions and Hydrogen-Bonding Networks in (<i>o</i>-Aminoanilinium)&ndash;(Crown Ethers)&ndash;[PMo₁₂O₄₀]^4&minus; Crystals (2013)
  • Author(s): Daigoro Endo, Tomoyuki Akutagawa, Kazuya Kubo, Shin-ichiro Noro, Leroy Cronin, Takayoshi Nakamura
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 85 Issue: 3 Pages: 2249-2249
  • DOI: 10.1246/bcsj.20110371
  • NAID: 130004153043
  • Peer Reviewed
• [Journal Article] Hydrogen-Bonded Maleate Counter Anions in Tetrathiafulvalene Crystals (2012)
  • Author(s): Subbalakshmi Jayanty, Tomoyuki Akutagawa,* Takayoshi Nakamura
  • Journal Title: Cryst. Eng. Commun. Volume: 14 Pages: 3875-3881
  • DOI: 10.1039/c2ce25050k
  • Peer Reviewed
• [Journal Article] [Ni(dmit)2]- Salt with Flexible Supramolecular Cation Rotator (2012)
  • Author(s): Q. Ye, P. P. Shi, Z. Q. Chen, T. Akutagawa, S. Noro, and T. Nakamura
  • Journal Title: Inorg. Chem. Commun Volume: 20 Pages: 219-224
  • DOI: 10.1016/j.inoche.2012.03.012
  • Peer Reviewed
• [Journal Article] Crystal structures and magnetic properties of (4,4 '-phenylazophenyl)-diammonium(crown ethers)[Ni(dmit)2]2 crystals (2012)
  • Author(s): Norihisa Hoshino, Kazuya Kubo, Takayoshi Nakamura, and Tomoyuki Akutagawa
  • Journal Title: Dalton Transactions Volume: 41 Pages: 12968-12975
  • DOI: 10.1039/c2dt30807j
  • Peer Reviewed
• [Journal Article] Crystal structures and magnetic properties of (4,4'-phenylazophenyl)diammonium(crown ethers)[Ni(dmit)2]2 crystals (2012)
  • Author(s): Kiyonori Takahashi, Norihisa Hoshino, Kazuya Kubo, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: Dalton Trans. Volume: 14 Pages: 5235-5241
  • DOI: 10.1039/c2ce25493j
  • Peer Reviewed
• [Journal Article] Incorporation of Cationic Electron Donor of Ni-pyridyl-tetrathiafulvalene with Anionic Electron Acceptor of Polyoxometalate (2012)
  • Author(s): Ryo Tsunashima, Takumi Matsumoto, Kei Kondo, Yoshihiko Suyama, Yukihiro Nishioka, Jun Kawamata, Shin-ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa , Katsuya Ishiguro
  • Journal Title: Dalton. Trans Volume: 41 Pages: 10060-10064
  • DOI: 10.1039/c2dt30398a
  • Peer Reviewed
• [Journal Article] Synthesis and Crystal Structure of a One-dimensional Cu(II) Coordination Polymer Bridged by Inorganic CH₃SO₃^&minus; Anions Using Werner-type Cu(II) Complexes as Building Blocks (2012)
  • Author(s): S. Noro, K. Kubo and T. Nakamura
  • Journal Title: Chem. Lett. Volume: 41 Issue: 8 Pages: 772-773
  • DOI: 10.1246/cl.2012.772
  • NAID: 130004426636
  • Peer Reviewed
• [Journal Article] Flexible cis-Cyclohexane-1,4-diammonium in Magnetic [Ni(dmit)2] Crystals (2012)
  • Author(s): Qiong Ye, Ping-Ping Shi, Zi-Qi Chen, Tomoyuki Akutagawa, Shin-ichiro Noro, Takayoshi Nakamura
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  • DOI: 10.1002/ejic.201200099
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure, and Adsorption Properties of Werner-type Cu(II) Complex [Cu(CF₃SO₃)₂(4-methylpyridine)₄] (2012)
  • Author(s): S. Noro, K. Fukuhara, K. Kubo and T. Nakamura
  • Journal Title: Chem. Lett. Volume: 41 Issue: 10 Pages: 1314-1316
  • DOI: 10.1246/cl.2012.1314
  • NAID: 130004426366
  • Peer Reviewed
• [Journal Article] Supramolecular Rotators of (Aniliniums)([18]crown-6) in Electrically Conducting [Ni(dmit)2] Crystals (2012)
  • Author(s): Norihisa Hoshino, Yuuya Yoshii, Kazuya Kubo, Masaki Aonuma, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: Inorganic Chemistry Volume: 51 Pages: 12968-12975
  • DOI: 10.1021/ic302093b
  • Peer Reviewed
• [Journal Article] Structural phase transitions induced by molecular motions within an (anilinium)(L-tartrate) ionic molecular crystal (2012)
  • Author(s): Yuuya Yoshii, Norihisa Hoshino, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: Crystal Eng. Commun. Volume: 14 Pages: 219-224
  • DOI: 10.1039/c2ce25945a
  • Peer Reviewed
• [Journal Article] Exploring the thermochromism of sulfite-embedded polyoxometalate capsules (2011)
  • Author(s): Ryo Tsunashima, De Liang Long, Toru Endo, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura, Raul Quesada Cabrera, Paul F.McMillan, Paul Kogerler, Leroy Cronin
  • Journal Title: Phys. Chem. Chem. Phys Volume: 13 Pages: 7295-7297
  • DOI: 10.1039/c1cp20074g
  • Peer Reviewed
• [Journal Article] Rational Construction of Wide Coordination Space and Control of Adsorption Properties in One-Dimensional Cu(II) Coordination Polymer (2011)
  • Author(s): S.Noro, K.Fukuhara, K.Kubo, T.Nakamura
  • Journal Title: Crystal Growth and Design Volume: 11 Pages: 2379-2385
  • DOI: 10.1021/cg2001392
  • Peer Reviewed
• [Journal Article] Hydrogen-Bonded Assemblies of Two-Electron Reduced Mixed-Valence [XMo12O40] (X = P and Si) with p-Phenylenediamines (2011)
  • Author(s): Tomoyuki Akutagawa, Fumito Kudo, Ryo Tsunashima, Shin-ichiro Noro; Leroy Cronin, Takayoshi Nakamura
  • Journal Title: Inorg. Chem Volume: 50 Pages: 6185-6192
  • DOI: 10.1021/ic200683e
  • Peer Reviewed
• [Journal Article] Polymorphs and Structural Phase Transition of [Ni(dmit)2]- Crystals Induced by Flexible (trans-Cyclohexane-1, 4-diammonium)(Benzo[18 ]crown-6)2 Supramolecule (2011)
  • Author(s): Qiong Ye, Tomoyuki Akutagawa, Nonhisa Hoshino, Takemitsu Kikuchi, Shin-ichiro Noro, Ren Gen Xiong, Takayoshi Nakamura
  • Journal Title: Crystal Growth and Design Volume: 11 Pages: 14442-14449
  • DOI: 10.1021/cg2007556
  • Peer Reviewed
• [Journal Article] 4-(cyanomethyl)anilinium Perchlorate: A New Displacive-Type Molecular Ferroelectric (2011)
  • Author(s): Hong-Ling Cai, Wen Zhang, Jia-Zhen Ge, Yi Zhang, Kunio Awaga, Takayoshi Nakamura, Ren Gen
  • Journal Title: Phys. Rev. Lett Volume: 107 Pages: 147601-147601
  • DOI: 10.1103/physrevlett.107.147601
  • Peer Reviewed
• [Journal Article] Structural Phase Transition Due to the Flexible Supramolecule of (4-cyanomethylanilinium)([18]crown-6) in [Ni(dmit)2]- Crystal (2011)
  • Author(s): Qiong Ye, Tomoyuki Akutagawa, Heng Yun Ye, Tian Hang, Jia Zhen Ge, Ren-Gen Xiong, Shin-ichiro Noro, Takayoshi Nakamura
  • Journal Title: Cryst. Eng. Commun Volume: 13 Pages: 6185-6191
  • DOI: 10.1039/c1ce05581j
  • Peer Reviewed
• [Journal Article] Huge Dielectric Response and Molecular Motions in Paddle-Wheel [CuII2 (Adamantylcarboxylate)4(DMF)2]･(DMF)2 (2011)
  • Author(s): Qiong Ye, Kiyonori Takahashi, Norihisa Hoshino, Takemitsu Kikuchi, Tomoyuki Akutagawa, Shin-ichiro Noro, Sadamu Takeda, Takayoshi Nakamura
  • Journal Title: Chem. Eur. J. Volume: 17 Pages: 14442-14449
  • DOI: 10.1002/chem.201101743
  • Peer Reviewed
• [Journal Article] Supramolecular Cations of the m-fluoroanilinium(dibenzo[18]crown-6) in Ferromagnetic Salt (2011)
  • Author(s): Toru Endo, Tomoyuki Akutagawa, Shin-ichiro Noro, Takayoshi Nakamura
  • Journal Title: Dalton Trans. Volume: 40 Pages: 1491-1496
  • DOI: 10.1039/c0dt01140a
  • Peer Reviewed
• [Journal Article] An Imidazolate- and Azide-Bridged Copper(II) Coordination Polymer Consisting of Alternating Di- and Mononuclear Units (2011)
  • Author(s): Ken-ichi Sakai, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Eur.J.Inorg.Chem. Pages: 116-120
  • DOI: 10.1002/ejic.201000835
  • Peer Reviewed
• [Journal Article] An Imidazolate- and Azide-Bridged Copper(II) Coordination Polymer Consisting of Alternating Di- and Mononuclear Units (2011)
  • Author(s): Shin-ichiro Noro, Tomonori Ohba, Katsuo Fukuhara, YYukiko Takahashi, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Eur. J. Inorg. Chem. Volume: 40 Pages: 116-120
  • DOI: 10.1039/c0dt01129k
  • Peer Reviewed
• [Journal Article] Structural Phase Transition Due to the Flexible Supramolecule of (4-cyanomethylanilinium) ([18]crown-6) in [Ni(dmit)2]-Crystal (2011)
  • Author(s): Qiong Ye, *Tomoyuki Akutagawa, Heng Yun Ye, Tian Hang, Jia Zhen Ge, Ren-Gen Xiong, Shin-ichiro Noro, *Takayoshi Nakamura
  • Journal Title: Cryst.Eng.Commun. Volume: 13 Pages: 6185-6191
  • Peer Reviewed
• [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: Hiroshima
  • Year and Date: 2014-03-10
  • 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] Supramolecular Rotators for Ferroelectrics and Multiferroics (2013)
  • Author(s): T. Nakamura, S. Yoshitake, K. Kubo, S. Noro and T. Akutagawa
  • Organizer: The 15th Asian Chemical Congress
  • Place of Presentation: Sentosa, Singapore
  • Year and Date: 2013-08-21
  • Invited
• [Presentation] Molecular Multiferroics Based on Supramolecular Rotators (2012)
  • Author(s): T. Nakamura, M. Yoshitake, K. Kubo and S. Noro
  • Organizer: 8th IUPAC International Conference on Novel Materials and their Synthesis (NMS-VIII) & 22nd International Symposium on Fine Chemistry and Functional Polymers (FCFP-XXII)
  • Place of Presentation: Xi'an, China
  • Year and Date: 2012-10-17
• [Presentation] Ferroelectrics and Multiferroics based on Supramolecular Rotators (2011)
  • Author(s): T. Nakamura
  • Organizer: the third RIES-CIS Symposium
  • Place of Presentation: Hsinchu, Taiwan
  • Year and Date: 2011-10-28
  • Invited
• [Presentation] Ferroelectrics and Multiferroics based on Supramolecular Rotators (2011)
  • Author(s): T.Nakamura
  • Organizer: the third RIES-CIS Symposium
  • Place of Presentation: National Chiao Tung University (Taiwan)(招待講演)
  • Year and Date: 2011-10-28
• [Presentation] Organic-Inorganic Hybrid Systems toward "Dynamic" Functional Materials (2011)
  • Author(s): T.Nakamura
  • Organizer: 1st Discussion Symposium on 'Inorganic Biology and Protocells : Engineering Artificial Life'
  • Place of Presentation: University of Glasgow (UK)(招待講演)
  • Year and Date: 2011-09-13
• [Presentation] Organic ‐ Inorganic Hybrid Systems toward " Dynamic" Functional Materials (2011)
  • Author(s): T. Nakamura
  • Organizer: 1 st Discussion Symposium on ' Inorganic Biology and Protocells : Engineering Artificial Life'
  • Place of Presentation: Glasgow, UK
  • Year and Date: 2011-09-09
  • Invited