Development of single-component molecular conductors by using extended TTF-type dithiolate ligands with freedom of movement

• Project/Area Number: 17K05846
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Functional solid state chemistry
• Research Institution: Nihon University
• Principal Investigator: ZHOU Biao 日本大学, 文理学部, 教授 (80434067)
• Project Period (FY): 2017-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2020: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2019: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
• Keywords: 単一分子性伝導体 / ディラック電子系 / 分子運動自由度 / 拡張TTFジチオレン配位子 / 伝導性 / 磁性 / 分子配列

Outline of Final Research Achievements

The single-component molecular conductors are newly emerging molecular materials, which have brought about diverse electronic phases originating from intramolecular multi-orbitals. The single-component molecular conductors [M(dmdt)2] (M = Ni, Pd, Pt) systems, are sought-after ambient-pressure molecular massless Dirac materials. Band calculations based on first-principles density functional theory reveal three-dimensional Dirac nodal lines lying approximately at the Fermi level. Temperature-insensitive conductivity and temperature-dependent spin susceptibility nearly vanishing at low temperature, in conjunction with the band-structure calculations, indicate that [M(dmdt)2] systems host strongly correlated massless Dirac electrons with nodal lines at ambient pressure, not previously substantiated in molecular materials.

Academic Significance and Societal Importance of the Research Achievements

単一分子性伝導体により常圧分子性ディラック電子系が実現されたことから、他の高圧分子性ディラック系では不可能な物性測定を容易に行う事が出来る。常圧下で種々の物性測定により、分子性ディラック電子系の物理的な性質を明らかにすることがひとつの鍵となる。また、単一分子性伝導体の中心金属の違いにより電子物性が大きく異なる特徴があることから、分子性物質の電子構造や、機能を理解するのに重要な情報を提供できると考えられる。

Research Products

• [Journal Article] Single-Component Molecular Conductors ? Multi-Orbital Correlated π-d Electron Systems (2021)
  • Author(s): Kobayashi Akiko、Zhou Biao、Takagi Rina、Miyagawa Kazuya、Ishibashi Shoji、Kobayashi Akito、Kawamura Taiki、Nishibori Eiji、Kanoda Kazushi
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 94 Issue: 10 Pages: 2540-2562
  • DOI: 10.1246/bcsj.20210230
  • NAID: 130008117228
  • Peer Reviewed / Open Access
• [Journal Article] Possible Spin-Density Wave on Fermi Arc of Edge State in Single-Component Molecular Conductors [Pt(dmdt)₂] and [Ni(dmdt)₂] (2021)
  • Author(s): Kawamura Taiki、Zhou Biao、Kobayashi Akiko、Kobayashi Akito
  • Journal Title: Journal of the Physical Society of Japan Volume: 90 Issue: 6 Pages: 064710-064710
  • DOI: 10.7566/jpsj.90.064710
  • NAID: 40022591363
  • Peer Reviewed
• [Journal Article] Syntheses, Structures, and Physical Properties of Neutral Gold Dithiolate Complex, [Au(etdt)2]・THF (2020)
  • Author(s): Sakaguchi Kazuha、Zhou Biao、Idobata Yuki、Kamebuchi Hajime、Kobayashi Akiko
  • Journal Title: Crystals Volume: 10 Issue: 11 Pages: 1001-1001
  • DOI: 10.3390/cryst10111001
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Microscopic Observation of π Spin Polarization by d Localized Spin in λ Type BETS Based Organic Superconductors (2020)
  • Author(s): Hiraki Ko-ichi、Takahashi Toshihiro、Akiba Hiroshi、Nishio Yutaka、Zhou Biao
  • Journal Title: Crystals Volume: 10 Issue: 11 Pages: 1055-1055
  • DOI: 10.3390/cryst10111055
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Spontaneous Antiferromagnetic Ordering in a Single Layer of (BETS)2GaCl4 Organic Superconductor (2020)
  • Author(s): Hassanien Abdou、Zhou Biao、Kobayashi Akiko
  • Journal Title: Advanced Electronic Materials Volume: 6 Issue: 10 Pages: 2000461-2000461
  • DOI: 10.1002/aelm.202000461
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Multiorbital antiferromagnetic metal induced by intramolecular self-doping (2020)
  • Author(s): Takagi Rina、Gangi Hiro、Miyagawa Kazuya、Nishibori Eiji、Kasai Hidetaka、Seo Hitoshi、Zhou Biao、Kobayashi Akiko、Kanoda Kazushi
  • Journal Title: Physical Review Research Volume: 2 Issue: 3 Pages: 033321-033321
  • DOI: 10.1103/physrevresearch.2.033321
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Tight-Binding Model and Electronic Property of Dirac Nodal Line in Single-Component Molecular Conductor [Pt(dmdt)(2)] (2020)
  • Author(s): Kawamura Taiki, Ohki Daigo, Zhou Biao, Kobayashi Akiko, Kobayashi Akito
  • Journal Title: JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN Volume: 89 Issue: 7 Pages: 074704-074704
  • DOI: 10.7566/jpsj.89.074704
  • NAID: 40022283421
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Nickel-Catalyzed Asymmetric Friedel?Crafts Propargylation of 3-Substituted Indoles with Propargylic Carbonates Bearing an Internal Alkyne Group (2020)
  • Author(s): Miyazaki Yusuke、Zhou Biao、Tsuji Hiroaki、Kawatsura Motoi
  • Journal Title: Organic Letters Volume: 22 Issue: 5 Pages: 2049-2053
  • DOI: 10.1021/acs.orglett.0c00465
  • Peer Reviewed
• [Journal Article] Synthesis of substituted benzo[b][1,4]oxazepine derivatives by the reaction of 2-aminophenols with alkynones (2020)
  • Author(s): Oshimoto Kohei、Zhou Biao、Tsuji Hiroaki、Kawatsura Motoi
  • Journal Title: Organic & Biomolecular Chemistry Volume: 18 Issue: 3 Pages: 415-419
  • DOI: 10.1039/c9ob02450f
  • Peer Reviewed
• [Journal Article] C13 NMR evidence for strong electron correlation and antiferromagnetic order in the single-component molecular material Pd(tmdt)2 (2019)
  • Author(s): Takahashi Taiga、Sunami Keishi、Miyagawa Kazuya、Takagi Rina、Zhou Biao、Kobayashi Akiko、Kanoda Kazushi
  • Journal Title: Physical Review B Volume: 100 Issue: 7 Pages: 075117-075117
  • DOI: 10.1103/physrevb.100.075117
  • Peer Reviewed
• [Journal Article] Single-component molecular conductor [Pt(dmdt)2];a three-dimensional ambient-pressure molecular Dirac electron system (2019)
  • Author(s): Biao Zhou, Shoji Ishibashi, Tatsuru Ishii, Takahiko Sekine, Ryosuke Takehara, Kazuya Miyagawa, Kazushi Kanoda, Eiji Nishibori and Akiko Kobayashi
  • Journal Title: Chemical Communications Volume: 55 Issue: 23 Pages: 3327-3330
  • DOI: 10.1039/c9cc00218a
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Ring-Puckering Motion of Azetidinium Cations in a Metal-Organic Perovskite [(CH2)3NH2][M(HCOO)3] (M = Zn, Mg) - A Thermal and 1H NMR Relaxation Study (2019)
  • Author(s): Tetsuo Asaji, Yoshiharu Ito, Hiroki Fujimori, Biao Zhou
  • Journal Title: The Journal of Physical Chemistry C Volume: 123 Issue: 7 Pages: 4291-4298
  • DOI: 10.1021/acs.jpcc.8b11789
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Nickel-Catalyzed Asymmetric Propargylic Amination of Propargylic Carbonates Bearing an Internal Alkyne Group (2018)
  • Author(s): Kouichi Watanabe, Yusuke Miyazaki, Masataka Okubo, Biao Zhou, Hiroaki Tsuji, and Motoi Kawatsura
  • Journal Title: Organic Letters Volume: 20 Issue: 17 Pages: 5448-5451
  • DOI: 10.1021/acs.orglett.8b02325
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Magnetocaloric Effect in Layered Organic Conductor lambda-(BETS)2FeCl4 (2018)
  • Author(s): Shiori Sugiura, Kazuo Shimada, Naoya Tajima, Yutaka Nishio, Taichi Terashima, Takayuki Isono, Reizo Kato, Biao Zhou, Shinya Uji
  • Journal Title: Journal of the Physical Society of Japan Volume: 87 Issue: 4 Pages: 044601-044601
  • DOI: 10.7566/jpsj.87.044601
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Double amination of 2-fluoroallylic acetates by palladium catalysts (2018)
  • Author(s): Yukiko Tsuchi, Hirotaka Watanabe, Masaki Kogawa, Biao Zhou, Hiroaki Tsuji, Motoi Kawatsura
  • Journal Title: Tetrahedron Letters Volume: 59 Issue: 13 Pages: 1264-1267
  • DOI: 10.1016/j.tetlet.2018.02.047
  • Peer Reviewed
• [Journal Article] Antiferromagnetic Mott insulating state in the single-component molecular material Pd(tmdt)2 (2017)
  • Author(s): Rina Takagi, Dita Puspita Sari, Saidah Sakinah Mohd-Tajudin, Retno Ashi, Isao Watanabe, Shoji Ishibashi, Kazuya Miyagawa, Satomi Ogura, Biao Zhou, Akiko Kobayashi, and Kazushi Kanoda
  • Journal Title: Physical Review B Volume: 96 Issue: 21 Pages: 214432-214432
  • DOI: 10.1103/physrevb.96.214432
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Dielectric Properties of Methanol Molecules Incorporated in Porous Coordination Polymer Crystal, [La2Cu3(IDA)6] (IDA = [NH(CH2COO)2]2-) (2017)
  • Author(s): Yuji Imai, Biao Zhou, Akiko Kobayashi
  • Journal Title: Accounts of Materials & Surface Research Volume: 2 Pages: 101-109
  • Peer Reviewed
• [Journal Article] Spin-gapped Mott insulator with the dimeric arrangement of twisted molecules Zn(tmdt)2 (2017)
  • Author(s): Rina Takagi, Hiro Gangi, Kazuya Miyagawa, Biao Zhou, Akiko Kobayashi, and Kazushi Kanoda
  • Journal Title: Physical Review B Volume: 95 Issue: 22 Pages: 224427-224427
  • DOI: 10.1103/physrevb.95.224427
  • Peer Reviewed
• [Journal Article] Regioselective Three-Component Coupling by the Palladium-Catalyzed Reaction of 2-Fluoroallylic Acetates with Phenols and Imides (2017)
  • Author(s): Kogawa, M.; Watanabe, H.; Yamamoto, M.; Tsuchi, Y.; Zhou, B.; Kawatsura, M.
  • Journal Title: Synlett Volume: 28 Issue: 09 Pages: 2071-1074
  • DOI: 10.1055/s-0036-1588143
  • Peer Reviewed
• [Journal Article] Internal Field Effect on Vortex States in Layered Organic Superconductor lambda-(BETS)2Fe1-xGaxCl4 (x=0.37) (2017)
  • Author(s): S. Uji, T. Terashima, T. Konoike, T. Yamaguchi, S. Yasuzuka, A. Kobayashi, B. Zhou
  • Journal Title: Physical Review B Volume: 95 Issue: 16 Pages: 165133-165133
  • DOI: 10.1103/physrevb.95.165133
  • Peer Reviewed / Int'l Joint Research
• [Presentation] 単一分子性伝導体[M(dmdt)2] (M = Au, Zn)の構造と物性 (2021)
  • Author(s): 大野智世、亀渕萌、周彪
  • Organizer: 日本錯体化学会第71回討論会
• [Presentation] 柔軟な配位子t-1,4-CHDCを導入した、Cu(Ⅱ)錯体の合成と磁気特性 (2021)
  • Author(s): 村田浩平、亀渕萌、周彪
  • Organizer: 日本錯体化学会第71回討論会
• [Presentation] プロトン及び強い水素結合相互作用を有する純有機分子性伝導体の構造と物性 (2021)
  • Author(s): 森町勇人、亀渕萌、周彪
  • Organizer: 日本錯体化学会第71回討論会
• [Presentation] 単一成分分子性導体[M(dmdt)2] (M = Pt, Ni)の磁気的性質 (2021)
  • Author(s): 川村泰喜、周彪、小林昭子、小林晃人
  • Organizer: 日本物理学会2021年秋季大会
• [Presentation] 反強磁性単一分子種伝導体Pd(tmdt)2の圧力下における量子臨界的挙動 (2021)
  • Author(s): 須波圭史、高橋泰賀、宮川和也、周彪、小林昭子、鹿野田一司
  • Organizer: 日本物理学会2021年秋季大会
• [Presentation] 単一成分分子性導体中のディラックノーダルライン系における電子相関効果 (2021)
  • Author(s): 川村泰喜、周彪、小林昭子、小林晃人
  • Organizer: 日本物理学会第76回年次大会
• [Presentation] Dirac nodal line物質M(dmdt)2 (M = Ni, Pt)の13C-NMR研究 (2021)
  • Author(s): 関根孝彦、須波圭史、宮川和也、秋元健汰、周彪、石橋章司、小林昭子、鹿野田一司
  • Organizer: 日本物理学会第76回年次大会
• [Presentation] ポーラス結晶に取り込まれたゲスト分子に由来する誘電特性 (2020)
  • Author(s): 周彪
  • Organizer: 第56回熱測定討論会
  • Invited
• [Presentation] 単一成分分子性導体[Pt(dmdt)2]のエッジにおける電子相関効果 (2020)
  • Author(s): 川村泰喜、周彪、小林昭子、小林晃人
  • Organizer: 日本物理学会2020年秋季大会
• [Presentation] 純有機単一分子性伝導体[H(etdc)]の合成、構造および物性 (2020)
  • Author(s): 中島良太、周彪
  • Organizer: 日本化学会第100春季年会
• [Presentation] 単一分子性伝導体[M(etdt)2] (M = Ni, Au)の合成および物性について (2020)
  • Author(s): 坂口一葉、周彪
  • Organizer: 日本化学会第100春季年会
• [Presentation] 単一分子性伝導体[Ni(dmdt)2]の合成と構造 (2020)
  • Author(s): 秋元健汰、周、彪
  • Organizer: 日本化学会第100春季年会
• [Presentation] Synthesis, structure and magnetic properties of a manganese complex with extended-tetrathiafulvalene dicarboxylate ligand (2020)
  • Author(s): K. Kajimura, B. Zhou
  • Organizer: 日本化学会第100春季年会
• [Presentation] (1α,3α,5α)-1,3,5,-シクロヘキサントリカルボン酸を用いたMn(II)ポーラス結晶の合成、構造及び物性 (2020)
  • Author(s): 塚原直輝、周彪
  • Organizer: 日本化学会第100春季年会
• [Presentation] λ-BETS2FeCl4系の金属－絶縁体転移 (2019)
  • Author(s): 峯沢文弥、田嶋尚也、西尾豊、周彪、加藤礼三
  • Organizer: 日本物理学会2019年秋季大会
• [Presentation] 常圧masslessディラック電子系Pt(dmdt)2の13C NMR測定 (2019)
  • Author(s): 関根孝彦、須波圭史、竹原陵介、宮川和也、周彪、小林昭子、鹿野田一司
  • Organizer: 日本物理学会2019年秋季大会
• [Presentation] Single-Component Molecular Conductor [Pt(dmdt)2]-An Ambient Molecular Dirac Material (2019)
  • Author(s): B. Zhou, S. Ishibashi, T. Ishii, T. Sekine, R. Takehara, K. Miyagawa, K. Kanoda, E. Nishibori, A. Kobayashi
  • Organizer: The 13th International Symposium on Crystalline Organic Metals Superconductors and Ferromagnets (ISCOM2019)
  • Int'l Joint Research
• [Presentation] Synthesis, Structures, and Properties of Novel Molecular Conductors Based on Extended-Tetrathiafulvalene Dicarboxylate Donors (2019)
  • Author(s): R. Nakajima, B. Zhou
  • Organizer: The 13th International Symposium on Crystalline Organic Metals Superconductors and Ferromagnets (ISCOM2019)
  • Int'l Joint Research
• [Presentation] 拡張型TTFジカルボン酸配位子を有するコバルト錯体の構造と物性 (2019)
  • Author(s): 中島良太、周彪
  • Organizer: 日本化学会第99春季年会
• [Presentation] 単一分子種伝導体Zn(tmdt)2の圧力下13C-NMR測定 (2019)
  • Author(s): 高橋泰賀、須波圭史、宮川和也、周彪、小林昭子、鹿野田一司
  • Organizer: 日本物理学会第74回年次大会
• [Presentation] 磁場誘起超伝導体κ-(BETS)2FeBr4の磁束状態 (2018)
  • Author(s): 杉浦栞理、鴻池貴子、寺嶋太一、周彪、宇治進也
  • Organizer: 日本物理学会2018年秋季大会
• [Presentation] 単一分子種伝導体Pd(tmdt)2の13C-NMR測定 (2018)
  • Author(s): 高橋泰賀、須波圭史、宮川和也、高木里奈、周彪、小林昭子、鹿野田一司
  • Organizer: 日本物理学会第73回年次大会
• [Presentation] dmit-(COOH)2を用いたマンガン及びコバルト錯体の合成と構造 (2018)
  • Author(s): 中島良太、周彪
  • Organizer: 日本化学会第98春季年会
• [Presentation] A New Series of Single-Component Molecular Conductors, [M(dmdt)2] (M = Ni, Pd, Pt, Au) (2017)
  • Author(s): Biao Zhou
  • Organizer: The 12th International Symposium on Crystalline Organic Metals Superconductors and Ferromagnets (ISCOM2017)
  • Int'l Joint Research