Development of ferroelectrics based on molecular rotators

2013 Fiscal Year Final Research Report

• 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
• Keywords: 分子ローター / 強誘電性 / 超分子 / クラウンエーテル / 磁性

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] 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
  • Peer Reviewed
• [Journal Article] Gold Nanoparticle Assemblies Stabilized by Bis(phthalocyaninato)lanthanide(III) Complexes through van der Waals Interactions (2014)
  • Author(s): Y. Noda, S. Noro, T. Akutagawa and T. Nakamura
  • Journal Title: Scientific Reports Volume: 4 Pages: 3758
  • DOI: 10.1038/srep03758
  • Peer Reviewed
• [Journal Article] Molecular Motion in Pyridazinium/Crown Ether Supramolecular Cation Salts of a Nickel Dithiolene Complex (2013)
  • Author(s): Z. Liu, K. Kubo, L. Lin, N. Hoshino, S. Noro, T. Akutagawa and T. Nakamura
  • Journal Title: Dalton Transactions Volume: 42 Pages: 2930-2939
  • DOI: 10.1039/c2dt32542j
  • Peer Reviewed
• [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, Y. Hijikata, M. Inukai, T. Fukushima, S. Horike, M. Higuchi, S. Kitagawa, T. Akutagawa and T. Nakamura
  • Journal Title: Inorg. Chem. Volume: 52 Pages: 280-285
  • DOI: 10.1021/ic301823j
  • Peer Reviewed
• [Journal Article] (3-Fluoro-4-methoxyanilinium)+([18]Crown-6) Supramolecular Cation Salt of Ferromagnetic [MnCrIIICrII(oxalate)3] (2013)
  • Author(s): T. Endo, K. Kubo, M. Yoshitake, S. Noro, T. Akutagawa and T. Nakamura
  • Journal Title: Chem. Lett Volume: 42 Pages: 137-139
  • DOI: 10.1246/cl.2013.137
  • 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): K. Kubo, Y. N. Yan, S. Noro, T. Akutagawa and T. 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
  • 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 Pages: 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: 5630-5635
  • DOI: 10.1021/ic400276c
  • 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 Pages: 11100-11110
  • DOI: 10.1039/c3dt51104a
  • Peer Reviewed
• [Journal Article] Graphene Oxide Nanosheet with High Proton Conductivity (2013)
  • Author(s): M. R. Karim, K. Hatakeyama, T. Matsui, H. Takehira, T. Taniguchi, M. Koinuma, Y. Matsumoto, T. Akutagawa, T. Nakamura and S. Noro
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Pages: 8097-8100
  • DOI: 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 Pages: 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, X. M. Ren, T. Akutagawa, J. Kishine, M. Fujisawa, A. Asakura, S. Okubo H. Ohta and T. Nakamura
  • Journal Title: Dalton Trans. Volume: 42 Pages: 15263-15266
  • DOI: 10.1039/c3dt52249k
  • Peer Reviewed
• [Journal Article] Hydrogen-Bonded Maleate Counter Anions in Tetrathiafulvalene Crystals (2012)
  • Author(s): S. Jayanty, T. Akutagawa and T. Nakamura
  • Journal Title: Cryst. Eng. Commun. Volume: 14 Pages: 3875-3881
  • DOI: 10.1039/c2ce25050k
  • Peer Reviewed
• [Journal Article] Molecular Motions and Hydrogen-Bonding Networks in (o-Aminoanilinium)-(Crown Ethers)-[PMo12O40]4- Crystals (2012)
  • Author(s): D. Endo, T. Akutagawa, K. Kubo, S. Noro, L. Cronin and T. Nakamura
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 85 Pages: 305-315
  • DOI: 10.1246/bcsj.20110371
  • 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): N. Hoshino, K. Kubo, T. Nakamura and T. Akutagawa
  • Journal Title: Dalton Transactions Volume: 41 Pages: 9297-9303
  • DOI: 10.1039/c2dt30807j
  • Peer Reviewed
• [Journal Article] Cation-Anion Packing and Molecular Motion in (m-fluoroanilinium)(dibenzo[18]crown-6)[Ni(mn t)2]-(CH3CN)0.25 Crystals (2012)
  • Author(s): K. Takahashi, N. Hoshino, K. Kubo, T. Nakamura and T. Akutagawa
  • Journal Title: CrystEngComm Volume: 14 Pages: 5235-5241
  • DOI: 10.1039/c2ce25493j
  • Peer Reviewed
• [Journal Article] Incorporation of Cationic Electron Donor of Ni-pyridyltetrathiafulvalene with Anionic Electron Acceptor of Polyoxometalate (2012)
  • Author(s): R. Tsunashima, T. Matsumoto, N. Hoshino, W. Niiho, M. Kimura, K. Kondo, Y. Suyama, Y. Nishioka, J. Kawamata, S. Noro, T. Nakamura, T. Akutagawa and K. Ishiguro
  • Journal Title: Dalton Transactions 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- Anions Using Werner-type Cu(II) Complexes as Building Blocks (2012)
  • Author(s): S. Noro, K. Kubo and T. Nakamura
  • Journal Title: Chem. Lett. 41 Pages: 772-773
  • DOI: 10.1246/cl.2012.772
  • Peer Reviewed
• [Journal Article] Flexible cis-Cyclohexane-1, 4-diammonium Ion in Magnetic [Ni(dmit)2] Crystals (2012)
  • Author(s): Q. Ye, P. Shi, Z. Chen, T. Akutagawa, S. Noro and T. Nakamura
  • Journal Title: Euro. J. Inorg. Chem Volume: 23 Pages: 3732-3739
  • 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 Pages: 1314-1316
  • DOI: 10.1246/cl.2012.1314
  • Peer Reviewed
• [Journal Article] Supramolecular Rotators of (Aniliniums)([18]crown-6) in Electrically Conducting [Ni(dmit)2] Crystals] (2012)
  • Author(s): N. Hoshino, Y. Yoshii, M. Aonuma, K. Kubo, T. Nakamura and T. Akutagawa
  • Journal Title: Inorg. Chem. 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): Y. Yoshii, N. Hoshino, T. Nakamura and T. Akutagawa
  • Journal Title: CrystEngCommun Volume: 14 Pages: 7458-7495
  • DOI: 10.1039/c2ce25945a
  • Peer Reviewed
• [Journal Article] Exploring the thermochromism of sulfite-embedded polyoxometalate capsules (2011)
  • Author(s): R. Tsunashima, D. L. Long, T. Endo, S. Noro, T. Akutagawa, T. Nakamura, R.Q. Cabrera, P. F. McMillan, P. Kogerler and L. 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 and 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): T. Akutagawa, F. Kudo, R. Tsunashima, S. Noro, L. Cronin and T. Nakamura
  • Journal Title: Inorg. Chem. Volume: 50 Pages: 6711-6718
  • 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): Q. Ye, T. Akutagawa, N. Hoshino, T. Kikuchi, S. Noro, R.G. Xiong and T. Nakamura
  • Journal Title: Crystal Growth and Design Volume: 11 Pages: 4175-4182
  • DOI: 10.1021/cg2007556
  • Peer Reviewed
• [Journal Article] 4-(cyanomethyl)anilinium Perchlorate : A New Displacive-Type Molecular Ferroelectric (2011)
  • Author(s): H.L. Cai, W. Zhang, J.Z. Ge, Y. Zhang, K. Awaga, T. Nakamura and R.G. Xiong
  • Journal Title: Phys. Rev. Lett. Volume: 107 Pages: 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): Q. Ye, T. Akutagawa. H. Y. Ye, T. Hang, J. Z. Ge, R. G. Xiong, S. Noro and T. 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): Q. Ye, K. Takahashi, N. Hoshino, T. Kikuchi, T. Akutagawa, S. Noro, S. Takeda and T. Nakamura
  • Journal Title: Chem. Eur. J Volume: 17 Pages: 14442-14449
  • DOI: 10.1002/chem.201101743
  • 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] 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] 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