Dielectric Anomaly and Structural Transition of Guest Molecules Incorporated in Nanoporous Crystals

• Project/Area Number: 21750153
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Functional materials chemistry
• Research Institution: Nihon University
• Principal Investigator: ZHOU Biao 日本大学, 文理学部, 助教 (80434067)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2011: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2010: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2009: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: ポーラス結晶 / 誘電性物質 / ゲスト分子 / 分子運動の自由度 / 誘電性 / リングパッカリング振動 / リラクサー / 有機ペロブスカイト / 擬似液体-固体転移

Research Abstract

Guest water molecules confined in channels of porous crystals [Cu_3La_2(IDA)_6](H_2O)_n exhibited antiferroelectric behaviors at high temperatures, and dielectric constants(ε) became very small at around 170 K. These puzzling temperature dependences ofεare consistent with the results of molecular dynamics simulations. And, metal-organic perovskite with four-membered ring azetidinium cations, [(CH_2)_3NH_2][Cu(HCOO)_3] exhibited a very broad and unprecedentedly large dielectric peak(～7×10^5 at 1 kHz) near 280 K. It is highly possible related to the ring-puckering instability of the four-membered ring ammonium cation.

Research Products

• [Journal Article] Anomalous Dielectric Behaviour and Thermal Motion of Water Molecules Incorporated in Porous Crystals (2012)
  • Author(s): Biao Zhou, Akiko Kobayashi, Zhe-Ming Wang, La-Sheng Long, and Hayao Kobayashi
  • Journal Title: Physica status solidi(c) Volume: 9 Issue: 5 Pages: 1216-1218
  • DOI: 10.1002/pssc.201100717
  • Peer Reviewed
• [Journal Article] Single-component Layered Molecular Conductor, [Au(ptdt)(2)] (2012)
  • Author(s): B.Zhou, H.Yajima, Y.Idobata, A.Kobayashi, T.Kobayashi, E.Nishibori, H.Sawa, H.Kobayashi
  • Journal Title: Chemistry Letters Volume: 41 Issue: 2 Pages: 154-157
  • DOI: 10.1246/cl.2012.154
  • NAID: 10030223247
  • Peer Reviewed
• [Journal Article] Molecular Alloy with Dilited Magnetic Moments. Molecular Kondo System (2012)
  • Author(s): Y. Idobata, B. Zhou, A. Kobayashi, H. Kobayashi
  • Journal Title: J. Amer. Chem. Soc. Volume: 134 Issue: 2 Pages: 871-874
  • DOI: 10.1021/ja210019y
  • Peer Reviewed
• [Journal Article] Charge Ordering and Carrier Generation by Air Oxidation of a Nickel Complex with Selenium-Containing Extended-Tetrathia fulvalenedithiolate Ligands (2012)
  • Author(s): H. Yajima, B. Zhou, E. Fujiwara, A. Kobayashi, H. Kobayashi
  • Journal Title: Inorg. Chem. Volume: 51 Issue: 5 Pages: 2731-2733
  • DOI: 10.1021/ic2026768
  • Peer Reviewed
• [Journal Article] Giant Dielectric Anomaly of Metal-Organic Perovskite with Four-membered Ring Ammonium Cation (2011)
  • Author(s): Biao Zhou, Yuji Imai, Akiko Kobayashi, Zhe-Ming Wang and Hayao Kobayashi
  • Journal Title: Angewandte Chemie International Edition Volume: 50 Issue: 48 Pages: 11441-11445
  • DOI: 10.1002/anie.201105111
  • Peer Reviewed
• [Journal Article] Anomalous Dielectric Behavior and Thermal Motion of Water Molecules Confined in Channels of Porous Coordination Polymer Crystals (2011)
  • Author(s): B.Zhou, et al
  • Journal Title: J.Amer.Chem.Soc. Volume: 133 Issue: 15 Pages: 5736-5739
  • DOI: 10.1021/ja200978u
  • Peer Reviewed
• [Journal Article] Dielectric Properties of Water Chains Incorporated in Porous Coordination Polymer Crystal [Cu(C_6H_4NO_2)_2] (2011)
  • Author(s): B.Zhou, et al
  • Journal Title: Chem.Lett. Volume: 40 Issue: 10 Pages: 1098-1100
  • DOI: 10.1246/cl.2011.1098
  • NAID: 130004426068
  • Peer Reviewed
• [Journal Article] Magnetic Single-Component Molecular Conductors Exhibiting Strongπ-d Interactions (2011)
  • Author(s): A. Kobayashi, B. Zhou, H. Kobayashi
  • Journal Title: Polyhedron Volume: 30 Issue: 18 Pages: 3298-3298
  • DOI: 10.1016/j.poly.2011.07.027
  • Peer Reviewed
• [Journal Article] Anomalous Dielectric Behavior and Thermal Motion of Water Molecules Confined in Channels of Porous Coordination Polymer Crystals (2011)
  • Author(s): B.Zhou, et al.
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 5736-5739
  • Peer Reviewed
• [Journal Article] Single-component Molecular Conductor [Cu(tmdt)_2] Containing Antiferromagnetic Heisenberg Chain (2010)
  • Author(s): B.Zhou, et al.
  • Journal Title: Inorg.Chem. Volume: 49 Pages: 6740-6747
  • Peer Reviewed
• [Journal Article] Mossbauer Spectroscopy and Magnetic Transition of λ-(BETS)_2FeCl_4 (2010)
  • Author(s): J.C.Waerenborgh, et al.
  • Journal Title: Phys.Rev.B Volume: 81
  • Peer Reviewed
• [Journal Article] Resistivity Measurements on TMTTeN and [Ni(ptdt)_2] above 20 GPa and Electrical and Structural Studies on [Au(tmdt)_2] (2010)
  • Author(s): H.Kobayashi, et al.
  • Journal Title: Physica B Volume: 405
  • Peer Reviewed
• [Journal Article] Evidence of Charge Disproportionation in λ Type BETS Based Organic Superconductors (2010)
  • Author(s): K.Hiraki, et al.
  • Journal Title: J.Phys.Soc.Jpn. Volume: 79
  • Peer Reviewed
• [Journal Article] Some electronic properties and morphological features of hybrid material DNA-SWCNT thin films (2010)
  • Author(s): Y.Maruyama, et al.
  • Journal Title: Solid State Commun. Volume: 150 Pages: 1584-1586
  • Peer Reviewed
• [Journal Article] Structural Anomalies Associated with Antiferromagnetic Transition of Single-Component Molecular Metal [Au(tmdt)_2] (2009)
  • Author(s): B.Zhou, et al.
  • Journal Title: Inorganic Chemistry 48 Pages: 10151-10157
  • Peer Reviewed
• [Journal Article] Single-component Molecular Conductor [Pt(tmdt)_2] (tmdt=trimethylenetetrathiafulvalenedithiolate)-An Advanced Molecular Metal Exhibiting High Metallicity (2009)
  • Author(s): B.Zhou, et al.
  • Journal Title: Advanced Materials 21 Pages: 3596-3600
  • Peer Reviewed
• [Journal Article] High-Pressure (up to 10.7GPa) Crystal Structure of Single-Component Molecular Meta1 [Au(tmdt)_2] (2009)
  • Author(s): Y.Okano, B.Zhou, et al.
  • Journal Title: Journal of the American Chemical Society 131 Pages: 7169-7174
  • Peer Reviewed
• [Journal Article] Possible Weakening of the Many-body Interactions in the Organic Quasi-two-dimensional metal α-(BETS)_2NH_4Hg(SCN)_4 (2009)
  • Author(s): S.I.Pesotskii, R.B.Lyubovskii, et al.
  • Journal Title: Journal of Experimental and Theoretical Physics 109 Pages: 664-666
  • Peer Reviewed
• [Journal Article] Structures and Physical Properties of Highly Conducting Single-Component Molecular Conductors Containing Se Atoms (2009)
  • Author(s): E.Fujiwara, B.Zhou, et al.
  • Journal Title: European Journal of Inorganic Chemistry 2009 Pages: 1585-1591
  • Peer Reviewed
• [Presentation] 層状構造を持つ単一成分分子性伝導体-[Au(ptdt)_2]の合成と物性 (2012)
  • Author(s): 周彪、矢島寛之、井戸端裕樹、小林昭子、小林速男
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学
  • Year and Date: 2012-03-28
• [Presentation] アゼチジンカチオンを含む有機ペロブスカイト型金属錯体の誘電異常 (2012)
  • Author(s): 今井勇二, 周彪, 小林昭子, 小林速男
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應義塾大学,日吉
• [Presentation] 新規な電子機能性を示す分子物質の開発.分子性稀薄磁性合金と巨大な誘電異常を示す有機ペロブスカイト (2012)
  • Author(s): 小林昭子, 周彪, 小林速男
  • Organizer: 新学術領域研究"分子自由度が拓く新物質科学"第6回領域会議
  • Place of Presentation: ホテル岩沼屋,仙台
• [Presentation] 金属錯体ポリマー結晶を用いた新しい誘電体の開発 (2011)
  • Author(s): 周彪、小林昭子、小林速男
  • Organizer: 分子アンサンブル2011
  • Place of Presentation: 理研
  • Year and Date: 2011-11-10
• [Presentation] 中心金属を銅とする単一分子性磁性伝導体[Cu(dmdt)_2]の低温構造と磁気転移 (2011)
  • Author(s): 周彪、井戸端裕樹、小林昭子、小林速男、崔亨波、加藤礼三
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2011-03-29
• [Presentation] 金属錯体ポリマー結晶を用いた新しい誘電体の開発 (2011)
  • Author(s): 周彪, 小林昭子, 小林速男
  • Organizer: 分子アンサンブル2011
  • Place of Presentation: 理研,和光
• [Presentation] Dielectric Properties of Water Molecules in Porous Crystal, [Ln_2Cu_3(IDA)_6]・nH_2O(Ln=La, Nd, Sm, Gd, Ho, Er ; n=9.3) (2011)
  • Author(s): Biao Zhou, Akiko Kobayashi and Hayao Kobayashi
  • Organizer: The 9th International Symposium on Crystalline Organic Metals, Superconductors and Ferromagnets(ISCOM2011)
  • Place of Presentation: Pozna., Poland
• [Presentation] 新規な電子機能性を示す分子物質の開発-単一分子性伝導体multi-frontierπ-d系と新しいポーラス誘電体 (2011)
  • Author(s): 小林昭子, 周彪, 小林速男
  • Organizer: 新学術領域研究"分子自由度が拓く新物質科学"第5回領域会議
  • Place of Presentation: 東京大学,本郷
• [Presentation] ポーラス結晶[Ln_2Cu_3(IDA)_6] nH_2O(Ln=La, Nd, Sm, Gd, Ho, Er ; n〓9.0)にとり込まれた水分子の誘電特性 (2011)
  • Author(s): 周彪, 小林昭子, 小林速男
  • Organizer: 新学術領域研究"分子自由度が拓く新物質科学"第4回領域会議
  • Place of Presentation: 東京大学,本郷
• [Presentation] Dielectric Properties of Water Molecules in Porous Crystal, [Ln_2Cu_3(IDA)_6]・nH_2O(Ln=La, Nd, Sm, Gd, Ho, Er; n〓9.3) (2011)
  • Author(s): B.Zhou, A.Kobayashi, H.Kobayashi
  • Organizer: The 9th International Symposium on Crystalline Organic Metals, Superconductors and Ferromagnets
  • Place of Presentation: Poznan, Poland
• [Presentation] ポーラス結晶[Ln_2Cu_3(IDA)_6]nH_2O(Ln=La,Nd,Sm,Gd,Ho,Er;n〓9.0)にとり込まれた水分子の誘電特性 (2011)
  • Author(s): 周彪、小林昭子、小林速男
  • Organizer: 新学術領域研究「分子自由度が拓く新物質科学」第4回領域会議
  • Place of Presentation: 東京
• [Presentation] ポーラス結晶[Ln_2Cu_3(IDA)_6]nH_2O(Ln=La,Nd,Sm,Gd,Ho,Er;n〓9.3)に取り込まれた水分子の誘電特性 (2010)
  • Author(s): 周彪、小林昭子、小林速男
  • Organizer: 私立大学戦略的基盤形成事業[構造制御および電子状態制御に基づく新物質の開発]2010年度研究発表会
  • Place of Presentation: 東京
  • Year and Date: 2010-12-25
• [Presentation] ポーラス結晶[Ln_2Cu_3(IDA)_6] nH_2O(Ln=La, Nd, Sm, Gd, Ho, Er ; n〓9.3)に取り込まれた水分子の誘電特性 (2010)
  • Author(s): 周彪, 小林昭子, 小林速男
  • Organizer: 私立大学戦略的基盤形成事業[構造制御および電子状態制御に基づく新物質の開発]2010年度研究発表会
  • Place of Presentation: 日本大学,桜上水
• [Presentation] 新規な電子機能を持つ分子物質の開発 (2010)
  • Author(s): 周彪, 小林昭子, 小林速男
  • Organizer: 私立大学戦略的基盤形成事業[構造制御および電子状態制御に基づく新物質の開発]2009年度研究発表会
  • Place of Presentation: 日本大学,桜上水
• [Presentation] Structural Anomalies of Single-component Magnetic Molecular Metal, [Au(tmdt)_2] (2010)
  • Author(s): B.Zhou, A.Kobayashi, H.Kobayashi
  • Organizer: The 12^<th> International Conference on Molecule-Based Magnets, ICMM2010
  • Place of Presentation: Beijing, China
• [Presentation] Synthesis of Single-component Molecular Conductors, [M(tmdt)_2], [M(etdt)_2] and [M(eodt)_2] (M=Au and Cu) (2010)
  • Author(s): B.Zhou, A.Kobayashi, H.Kobayashi
  • Organizer: International Conference on the Sciences and Technology of Synthetic Metals, ICSM2010
  • Place of Presentation: Kyoto, Japan
• [Presentation] A New Antiferromagnetic Molecular Conductor With Modified λ-type Structure, λ'-(BETS)_2FeBr_4 (2009)
  • Author(s): B.Zhou, et al.
  • Organizer: The 8^<th> International Symposium on Crystalline Organic Metals, Superconductors and Ferromagnets
  • Place of Presentation: 北海道
  • Year and Date: 2009-09-13
• [Presentation] Pressure and Temperature Dependences of Crystal Structure of Single-component Molecular Meta1, [Au(tmdt)_2] (2009)
  • Author(s): B.Zhou, et al.
  • Organizer: The 6^<th> National Conference on Coordination Chemistry (cum International Symposium on Coordination Chemistry)
  • Place of Presentation: Hong Kong
  • Year and Date: 2009-07-06
• [Presentation] ポーラス錯体結晶の誘電率の温度変化 (2009)
  • Author(s): 周彪, 小林昭子, 小林速男
  • Organizer: 私立大学戦略的基盤形成事業[構造制御および電子状態制御に基づく新物質の開発]キックオフミーティング
  • Place of Presentation: 日本大学,桜上水