Development of Novel Physical Properties of Supramolecular Charge Separation Compounds Containing Soft Matter Characters

• Project/Area Number: 20H01862
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 13030:Magnetism, superconductivity and strongly correlated systems-related
• Research Institution: Osaka University
• Principal Investigator: 中澤 康浩 大阪大学, 大学院理学研究科, 教授 (60222163)
• Project Period (FY): 2020-04-01 – 2024-03-31
• Project Status: Completed (Fiscal Year 2023)
• Budget Amount: ¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000); Fiscal Year 2023: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2022: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2021: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2020: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000)
• Keywords: 熱容量 / 磁気熱量効果 / 電荷分離 / 磁気冷却 / 誘電的性質 / 誘電特性 / 熱伝導 / 電荷揺らぎ / 電荷分離構造 / 熱容量測定 / 非平衡物性 / 分子性化合物 / 誘電異常 / 熱的性質

Outline of Research at the Start

両親媒性の有機配位子と金属イオンを用いた金属錯体、ドナー・アクセプター分子の複合塩等では、カチオンとアニオンがクラスターとして集積し、大きく電荷分離した特異な構造が形成される。これらの塩は、クラスターの間隙やそれらが繋がったキャビテー構造が柔らかく、揺らぎの大きな構造となる。こうした物質群で起こる量子性を伴う誘電的な特性や構造揺らぎ、外場印加で生じる構造変容、水や水和イオンの非平衡な運動に基づく固体物性を、熱測定、誘電測定、磁気・輸送現象測定などを通して追跡する。

Outline of Annual Research Achievements

本研究の目的は、空間的に広がったカチオン性、アニオン性のクラスターユニットが分離積層した構造や、ドナー性、アクセプター性の分子が異なった機能性ネットワークとして形成される電荷分離状態をもつ分子性化合物を対象に、強い分子間相互作用に根差した非平衡性や局所性をもった新しい物性開拓を行うことを目的としている。
アニオン型の骨格をもつM6[Rh4Zn4O(L-cys)12]・nH2O（RhZn系）の組成をもつ配位高分子を基礎構造に、カチオンクラスターの中心となるMサイトを希土類イオンGd3＋に単結晶―単結晶変換で置き換えたカチオンサイトがGd0.33[Gd4(OH)4(OAc)3]のような構造になる。これらの系ではカチオンの磁気クラスターがキュバン構造となり、間隙にはソフトな水分子が集積し超常磁性的な振る舞いを示した。Gd3+が密につまったこの多核ユニットでありながら、キュバンのフラストレーションによる長距離秩序の阻害により、低温まで大きなスピン縮退が残る。そのため、磁場の制御によって、低温で磁場に誘引された大きなエントロピー変化が現れる。磁気熱量効果、磁場中熱容量、磁化率等の測定を行い、磁気エントロピーを定量的な評価する実験を行い、Rh、Irを含んだアニオンフレームの系で、2Kにおいて15.15 Jkg-1K-1,17.49 Jkg-1K-1のエントロピーに相当する磁気冷却効果の発現を確認した。磁場中の熱容量測定からこの値が信頼性が高いことを検証した。
一方で、ドナーとアニオンの層状電荷分離構造をもつ分子性電荷移動錯体であるθ-(BEDT-TTF)2X（Xは1価のアニオン分子）における電荷秩序状態転移の近傍での熱測定を行い、転移の次元性とエントロピーを議論した。また、電荷がガラス状態に凍結すること伴う熱力学的なダイナミクスを作成した高感度交流熱測定によって検出した。

Research Progress Status

令和5年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和5年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] 核物理研究所(ポーランド)
• [Int'l Joint Research] 低温物理・低温工学研究所(ウクライナ)
• [Int'l Joint Research] 低温物理・低温工学研究所(ウクライナ)
• [Int'l Joint Research] Visva Bharati University(インド)
• [Int'l Joint Research] Inst. of Low Temp. Physics(ウクライナ)
• [Int'l Joint Research] Institute for Nuclear Physics(ポーランド)
• [Int'l Joint Research] Visva Bharati University(インド)
• [Int'l Joint Research] Institute of Nuclear Physics(ポーランド)
• [Int'l Joint Research] Inst. of Low Temp Phys.(ウクライナ)
• [Journal Article] Thermodynamic Analyses of Superconducting Gap Structures and Pairing Symmetries of Molecular Charge-Transfer Salts (2023)
  • Author(s): 今城周作、中澤康浩
  • Journal Title: Butsuri Volume: 78 Issue: 2 Pages: 79-84
  • DOI: 10.11316/butsuri.78.2_79
  • ISSN: 0029-0181, 2423-8872
  • Year and Date: 2023-02-05
  • Peer Reviewed
• [Journal Article] Correlation-driven organic 3D topological insulator with relativistic fermions (2023)
  • Author(s): Nomoto Tetsuya、Imajo Shusaku、Akutsu Hiroki、Nakazawa Yasuhiro、Kohama Yoshimitsu
  • Journal Title: Nature Communications Volume: 14 Issue: 1 Pages: 2130-2130
  • DOI: 10.1038/s41467-023-37293-3
  • Peer Reviewed / Open Access
• [Journal Article] Heat Capacity of Poly(N-vinylpyrrolidone) (2023)
  • Author(s): K. Ishikiriyama, K. Kondo, Y. Miyazaki, Y. Sasada, K. Sawada, R. Endo, N. Man, M. Nakano, and Y. Nakazawa
  • Journal Title: Thermochim. Acta Volume: 722 Pages: 1794561-14
  • DOI: 10.1016/j.tca.2023.179456
  • Peer Reviewed
• [Journal Article] Magnetic field induced transition in the charge-glass former θ－(BEDT－TTF)2CsCo(SCN)4 (2023)
  • Author(s): Nomoto Tetsuya、Yamashita Satoshi、Akutsu Hiroki、Nakazawa Yasuhiro
  • Journal Title: Physical Review B Volume: 107 Issue: 8 Pages: 085121-085121
  • DOI: 10.1103/physrevb.107.085121
  • Peer Reviewed
• [Journal Article] Magnetoelectric, spectroscopic, optical and elastic properties of Co-doped BaTiO3 ceramics (2023)
  • Author(s): R. Bujakiewicz-Koronska, L. Gondek, L. Vasylechko, M. Balanda, E. Juszynska-Galazka, M. Galazka, D. Majda, W. Piekarczyk, A. Zywczak, A. Cizman, M. Sitarz, P. Jelen, W. Salamon, P. Czaja, J. Jedryka, K. Koronski, A. Kalvane, K. Gornicka, E. Markiewicz, S. Yamashita and Y. Nakazawa
  • Journal Title: Journal of Alloys and Compounds Volume: 946 Pages: 1693441-17
  • DOI: 10.1016/j.jallcom.2023.169344
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Thermal conductivity measurement system for molecules-based compounds available in a wide temperature region (2023)
  • Author(s): L. Zhang, T. Nomoto, S. Yamashita, H. Akutsu, A.I. Krivchikov and Y. Nakazawa
  • Journal Title: Low Temp. Phys. Volume: 49 Issue: 5 Pages: 539-544
  • DOI: 10.1063/10.0017814
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Pseudogap formation in organic superconductors (2023)
  • Author(s): S. Imajo, T. Kobayashi, Y. Matsumura, T. Maeda, Y. Nakazawa, H. Taniguchi, and K. Kindo
  • Journal Title: Phys. Rev. Mater. Volume: 7 Pages: 1248031-7
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Thermodynamic properties of the Mott insulator-metal transition in a triangular lattice system without magnetic order (2023)
  • Author(s): Emre Yesil, Shusaku Imajo, Satoshi Yamashita, Hiroki Akutsu, Yohei Saito, Andrej Pustogow, Atsushi Kawamoto, and Yasuhiro Nakazawa
  • Journal Title: Phys. Rev. B Volume: 107 Issue: 4 Pages: 0451331-9
  • DOI: 10.1103/physrevb.107.045133
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Systematic study on thermal conductivity of organic triangular lattice systems (2022)
  • Author(s): T. Nomoto, S. Yamashita, H. Akutsu, Y. Nakazawa, and R. Kato
  • Journal Title: Phys. Rev. B Volume: 105 Issue: 24 Pages: 2451331-7
  • DOI: 10.1103/physrevb.105.245133
  • Peer Reviewed
• [Journal Article] Thermodynamic measurements of doped dimer-Mott organic superconductor under pressure (2022)
  • Author(s): Matsumura Y.、Yamashita S.、Akutsu H.、Nakazawa Y.
  • Journal Title: Low Temperature Physics Volume: 48 Issue: 1 Pages: 51-56
  • DOI: 10.1063/10.0008964
  • Peer Reviewed
• [Journal Article] Persistence of fermionic spin excitations through a genuine Mott transition in κ-type organics (2022)
  • Author(s): Imajo S.、Kato N.、Marckwardt R. J.、Yesil E.、Akutsu H.、Nakazawa Y.
  • Journal Title: Physical Review B Volume: 105 Issue: 12 Pages: 125130-125130
  • DOI: 10.1103/physrevb.105.125130
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] An Organic Quantum Spin Liquid with Triangular Lattice: Spinon Fermi Surface and Scaling Behavior (2022)
  • Author(s): T. Kusamoto, C. Ohde, S. Sugiura, S. Yamashita, R. Matsuoka, T.Terashima, Y. Nakazawa , H. Nishihara and S. Uji
  • Journal Title: Bull.Chem.Soc.Jpn. Volume: 95 Issue: 2 Pages: 306-313
  • DOI: 10.1246/bcsj.20210411
  • Peer Reviewed
• [Journal Article] Electronic Heat Capacity and Lattice Softening of Partially Deuterated Compounds of κ-(BEDT-TTF)2Cu[N(CN)2]Br (2022)
  • Author(s): Y. Matsumura, S. Imajo, S. Yamashita, H. Akutsu, and Y. Nakazawa
  • Journal Title: Crystals Volume: 12 Issue: 1 Pages: 21-12
  • DOI: 10.3390/cryst12010002
  • Peer Reviewed / Open Access
• [Journal Article] Electric dipole induced bulk ferromagnetism in dimer Mott molecular compounds (2021)
  • Author(s): Yoshimoto Ryo、Yamashita Satoshi、Akutsu Hiroki、Nakazawa Yasuhiro、Kusamoto Tetsuro、Oshima Yugo、Nakano Takehito、Yamamoto Hiroshi M.、Kato Reizo
  • Journal Title: Scientific Reports Volume: 11 Issue: 1 Pages: 13321-10
  • DOI: 10.1038/s41598-020-79262-6
  • Peer Reviewed / Open Access
• [Journal Article] Structural, magnetic and Mossbauer spectroscopic studies of the [Fe(3-bpp)2](CF3COO)2 complex: role of crystal packing leading to an incomplete Fe(ii) high spin [右矢印左矢印の記号] low spin transition (2021)
  • Author(s): Sugiyarto Kristian Handoyo、Onggo Djulia、Akutsu Hiroki、Reddy Varimalla Raghavendra、Sutrisno Hari、Nakazawa Yasuhiro、Bhattacharjee Ashis
  • Journal Title: CrystEngComm Volume: 23 Issue: 15 Pages: 2854-2861
  • DOI: 10.1039/d0ce01687j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Fermi Surface Structure and Isotropic Stability of Fulde-Ferrell-Larkin-Ovchinnikov Phase in Layered Organic Superconductor b″-(BEDT-TTF)2SF5CH2CF2SO3 (2021)
  • Author(s): S. Sugiura, H. Akutsu, Y. Nakazawa, T. Terashima, S. Yasuzuka, J. A. Schlueter, and S. Uji
  • Journal Title: Crystals Volume: 11 Issue: 12 Pages: 1525-1525
  • DOI: 10.3390/cryst11121525
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Lattice and Charge Fluctuations in a Molecular Superconductors (2021)
  • Author(s): T. Yamamoto, T. Naito, M. Uruichi, H. Akutsu, and Y. Nakazawa
  • Journal Title: J. Phys. Soc. Jpn. Volume: 90 Issue: 6 Pages: 0637081-5
  • DOI: 10.7566/jpsj.90.063708
  • NAID: 40022591115
  • Peer Reviewed
• [Journal Article] Experimental Heat Capacity of Low-Dimensional Systems: Carbon Nanotube and 1D Atomic and Molecular Chains of Adsorbates (2021)
  • Author(s): M. Barabashko and Y. Nakazawa
  • Journal Title: Netsu Solutei Volume: 48 Pages: 1641-7
  • NAID: 40022761068
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Variation of Electronic Heat Capacity of κ-(BEDT-TTF)2Cu[N(CN)2]Br Induced by Partial Substitution of Donor Layers (2020)
  • Author(s): Yesil Emre、Imajo Shusaku、Nomoto Tetsuya、Yamashita Satoshi、Akutsu Hiroki、Nakazawa Yasuhiro
  • Journal Title: Journal of the Physical Society of Japan Volume: 89 Issue: 7 Pages: 073701-073701
  • DOI: 10.7566/jpsj.89.073701
  • NAID: 40022283302
  • Peer Reviewed
• [Journal Article] Single Crystal Heat Capacity Measurement of Charge Glass Compound θ-(BEDT-TTF)2CsZn(SCN)4 Performed Under Current and Voltage Application (2020)
  • Author(s): K. Hino, T. Nomoto, S. Yamashita, and Y. Nakazawa
  • Journal Title: Crystals Volume: 10 Issue: 11 Pages: 10601-10
  • DOI: 10.3390/cryst10111060
  • Peer Reviewed / Open Access
• [Journal Article] Thermodynamic properties of glassy phonon states induced by strong electron correlations in θ-type organic charge transfer salts (2020)
  • Author(s): Nomoto T.、Yesil E.、Yamashita S.、Akutsu H.、Nakazawa Y.
  • Journal Title: Modern Physics Letters B Volume: 34 Issue: 19n20 Pages: 2040059-2040059
  • DOI: 10.1142/s021798492040059x
  • Peer Reviewed
• [Journal Article] Development of frequency tuning AC modulation method for high-pressure heat capacity measurements of molecules-based compounds (2020)
  • Author(s): Nomoto T.、Maruyama T.、Yamashita S.、Akutsu H.、Nakazawa Y.
  • Journal Title: Modern Physics Letters B Volume: 34 Issue: 19n20 Pages: 2040062-2040062
  • DOI: 10.1142/s021798492040062x
  • Peer Reviewed
• [Journal Article] Anisotropic Fully Gapped Superconductivity Possibly Mediated by Charge Fluctuations in a Nondimeric Organic Complex (2020)
  • Author(s): Imajo S.、Akutsu H.、Kurihara R.、Yajima T.、Kohama Y.、Tokunaga M.、Kindo K.、Nakazawa Y.
  • Journal Title: Physical Review Letters Volume: 125 Issue: 17 Pages: 177002-177002
  • DOI: 10.1103/physrevlett.125.177002
  • Peer Reviewed
• [Presentation] Thermodynamic properties of molecular dimer Mott system (2024)
  • Author(s): Y. Nakazawa
  • Organizer: Workshop on Molecular Solid State Science 3月29-30日 (愛媛大学)
• [Presentation] Molecular Superconductors and Their Thermodynamic Properties (2023)
  • Author(s): Y. Nakazawa
  • Organizer: The 10th International and 12th China-Japan Joint Symposium on Calorimetry and Thermal Analysis (CATS-2023) (Shandong, China), September 23
  • Int'l Joint Research / Invited
• [Presentation] Hole Doping in the Spin Liquid State of Organic Charge Transfer Complexes (2023)
  • Author(s): Y. Nakazawa, T. Nomoto, S. Imajo, S. Yamashita and H. Akutsu
  • Organizer: 3rd International Advanced Research Workshop Thermal Conductivity of solid states at low temperature (Oct. 25th 2023).
  • Int'l Joint Research / Invited
• [Presentation] Heat Capacity Measurements of Non-Ordered Spin States in Dimer-Mott Molecular Compounds (2023)
  • Author(s): Y. Nakazawa, E. Yesil, S. Imajo, S. Yamashita, and H. Akutsu
  • Organizer: The 26th International Conference on Chemical Thermodynamics (ICCT-2023) (Toyonaka (Hybrid)), July 30- August 4
  • Int'l Joint Research
• [Presentation] Pd(dmit)2電荷移動塩のスピン液体相と周辺相の熱伝導 (2023)
  • Author(s): 中澤康浩
  • Organizer: 日本物理学会第78回年次大会（仙台），9月16 -19日
  • Invited
• [Presentation] 分子性電荷移動塩のMott転移における相境界の熱力学的挙動 (2023)
  • Author(s): 中澤康浩，松村祐希，張 路明，今城周作，山下智史，圷 広樹
  • Organizer: 第59回熱測定討論会（東京)，10月24-26日
• [Presentation] Thermodynamics Related to the Mott-Hubbard Physics in Organic Conductors (2023)
  • Author(s): Y. Nakazawa
  • Organizer: Workshop of Research Center for Thermal and Entropic Science (Toyonaka), October 20
  • Int'l Joint Research
• [Presentation] Thermodynamic Properties around the Metal-Insulator Spin Phase Boundary in the Dimer-Mott Organic Compounds (2022)
  • Author(s): Y. Nakazawa, E. Yesil, S. Imajo, S. Yamashita and H. Akutsu
  • Organizer: Multiscale Phenomena in Condensed Matter (Multis 2022) (Online)
  • Int'l Joint Research
• [Presentation] Introduction of Calorimetry and its Application for Researches (2022)
  • Author(s): Y. Nakazawa
  • Organizer: Virtual Intercontinental Assembly on Calorimetry and Thermal Analysis (VIACTA2022)
  • Int'l Joint Research
• [Presentation] Quantum Features around the Mott Boundary in Organic pai-electrons Compounds (2022)
  • Author(s): Y. Nakazawa, Emre Yesil,Y. Matsumura, S. Imajo, S. Yamashita and H. Akutsu
  • Organizer: 2nd International Workshop Thermal Conductivity of Solid States at Low Temperatures
  • Int'l Joint Research / Invited
• [Presentation] 分子性電荷移動塩における金属絶縁体転移近傍の熱力学的性質 (2022)
  • Author(s): Emre Yesil，松村祐希，今城周作，山下智史，圷広樹，中澤康浩
  • Organizer: 第58回熱測定討論会（オンラインおよびハイブリット（東京））
• [Presentation] 二次元層状金属錯体の面内、面間熱伝導測定 (2022)
  • Author(s): 張 路明，山下智史，圷広樹，野本哲也，星野哲久，芥川智行，中澤康浩
  • Organizer: 第58回熱測定討論会（オンラインおよびハイブリット（東京））
• [Presentation] Magneto-caloric effect of frustrated metal complexes containing Gd ions (2022)
  • Author(s): Yu Zhang, Satoshi Yamashita, Hiroki Akutsu, Tetsuya Nomoto, Nobuto Yoshinari, Takumi Konno, and Yasuhiro Nakazawa
  • Organizer: 第58回熱測定討論会（オンラインおよびハイブリット（東京））
• [Presentation] 微小結晶熱伝導率測定装置の開発と層状有機分子の物性研究 (2022)
  • Author(s): 張 路明，山下智史，圷広樹，中澤康浩
  • Organizer: 分子科学討論会2022（横浜
• [Presentation] α-(BETS)2I3における2D-3Dクロスオーバーとカイラル磁気異常効果 (2022)
  • Author(s): 野本哲也, 今城周作, 圷広樹, 中澤康浩, 小濱芳允
  • Organizer: 日本物理学会 2022年秋季大会（ハイブリッド（東京）
• [Presentation] Thermal Conductivity of Organic Charge Transfer Complexes with Strong Correlation in 2D pai-Electrons Layers (2021)
  • Author(s): Y. Nakazawa
  • Organizer: The International Advanced Research Workshop “Thermal Conductivity of Sold State at Low Temperature” (Online)
  • Int'l Joint Research / Invited
• [Presentation] 熱測定による分子性電荷移動塩の物性研究 (2021)
  • Author(s): 中澤康浩
  • Organizer: 九州大学先導物質化学研究所セミナー（オンライン）
  • Invited
• [Presentation] 二次元ダイマー型電荷移動錯体の電子状態と量子相転移 (2021)
  • Author(s): 中澤康浩，Emre Yesil，今城周作，山下智史，圷 広樹
  • Organizer: 第57回熱測定討論会（オンライン）
• [Presentation] フラストレート系有機伝導体に対する低温熱伝導率測定 (2021)
  • Author(s): 野本哲也，山下智史，圷 広樹，中澤康浩，加藤礼三
  • Organizer: 第57回熱測定討論会（オンライン）
• [Presentation] 薄膜型装置の微小単結晶試料量に対する比熱測定 (2021)
  • Author(s): 宇野陽亮，中澤康浩，圷 広樹，山下智史
  • Organizer: 第57回熱測定討論会（オンライン）
• [Presentation] Thermodynamic Studies of Novel Molecular Ferromagnets in Dimer-Mott Charge Transfer Compounds (2020)
  • Author(s): Y. Nakazawa
  • Organizer: International Advanced Study Conference on Condensed Matter & Low Temperature Physics 2020 (CMLTP2020) (Online)
  • Int'l Joint Research / Invited
• [Presentation] Possibility to Tune Thermodynamic Parameters of Organic Spin Liquids Using Chemical Substitutions (2020)
  • Author(s): Y. Nakazawa
  • Organizer: International Symposium of Thermal and Entropic Science
  • Int'l Joint Research
• [Presentation] フラストレーションをもつ分子性電荷移動塩の電子状態 (2020)
  • Author(s): 中澤康浩，今城周作，Emre Yesil，山下智史，圷 広樹
  • Organizer: 第56回熱測定討論会（オンライン）
• [Presentation] 電荷フラストレート系theta-(BEDT-TTF)2CsCo(SCN)4における磁場誘起相転移 (2020)
  • Author(s): 野本哲也，山下智史，圷 広樹，中澤康浩
  • Organizer: 分子科学会オンライン討論会
• [Presentation] Low Temperature Heat Capacity Measurement of a Spin Liquid / Fermi Liquid Alloying System (2020)
  • Author(s): E. Yesil, Y. Saito, S. Yamashita, H. Akutsu, A. Kawamoto, and Y. Nakazawa
  • Organizer: 分子科学会オンライン討論会
• [Book] 熱量測定・熱分析ハンドブック 第3版 (2020)
  • Author(s): 中澤康浩（日本熱測定学会編，執筆分担）
  • Total Pages: 363
  • Publisher: 丸善
  • ISBN: 9784621305072
• [Remarks] 阪大化学熱学レポート
  • URL: https://www.chem.sci.osaka-u.ac.jp/lab/micro/
• [Remarks] 物性物理化学研究室
  • URL: http://www.chem.sci.osaka-u.ac.jp/lab/nakazawa/