層状分子磁石における動的π造形による物性制御

• Project Area: pi-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions
• Project/Area Number: 17H05137
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tohoku University
• Principal Investigator: 宮坂 等 東北大学, 金属材料研究所, 教授 (50332937)
• Project Period (FY): 2017-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000); Fiscal Year 2018: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2017: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
• Keywords: πー集積型錯体 / 層状分子磁石 / 動的π造形 / 分子吸脱着 / 磁気ーイオン制御 / 磁気-イオン制御

Outline of Annual Research Achievements

(I) 昨年度からの継続研究で、酸素を吸着して酸素の電子スピンを介した三次元磁気秩序を起こす多孔性磁石を開発し、論文として発表した（Nat. Commun.に発表）。ガス吸着で磁気相を変換する世界で初めての例であり、東北大学からプレスリリースするにも至った。この結果を始めとして、我々の層状磁石の多くが一般的なガス分子を吸脱着させることがわかってきた。現在数種の化合物について詳細に研究を開始しているが、ガス吸着により（１）構造変化を伴って格子の電子移動を誘発し、磁気相が変換する物質、（２）構造転移により層間距離や環境が変化することにより磁気相が変換される物質、（３）上記のように、酸素などの常磁性ゲスト分子の電子スピンを介した超交換相互作用により長距離筒所を作る物質、の全く新しい機構による３種の多孔性可変磁石を見出すに至っている。これらは、π造形という観点から見ると、dπ-pπの軌道重なりによる超交換相互作用の制御に位置し、「Dynamic π」及び「Dynamic spin」ということができる。今後益々新しい展開が大いに期待され、新しい分野が作られる可能性は高い。
(II) 熱的に多段階に電子移動相転移を示す新しい二次元化合物を見出した。また、この化合物はスポンジ磁石として振る舞い、結晶ー結晶転移を起こすことも明らかとなった（ACIEに発表）。この化合物も多孔性可変磁石やリチウムイオン電池による可変磁石になることが期待され、後者については相転移温度が120 Kを超える高相転移分子磁石を開発し、論文投稿中である。本系についても今後の展開が大いに期待される。

Research Progress Status

平成30年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成30年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Strong electronic influence of equatorial ligands on frontier orbitals in paddlewheel dichromium(ii,ii) complexes (2019)
  • Author(s): Huang Po-Jung、Natori Yoshiki、Kitagawa Yasutaka、Sekine Yoshihiro、Kosaka Wataru、Miyasaka Hitoshi
  • Journal Title: Dalton Transactions Volume: 48 Issue: 3 Pages: 908-914
  • DOI: 10.1039/c8dt04347g
  • Peer Reviewed
• [Journal Article] Magnetic Sponge with Neutral-Ionic Phase Transitions (2018)
  • Author(s): Wataru Kosaka, Yusuke Takahashi, Masaki Nishio, Keisuke Narushima, Hiroki Fukunaga, Hitoshi Miyasaka
  • Journal Title: Adv. Sci. Volume: 5 Issue: 2 Pages: 1700526-1700526
  • DOI: 10.1002/advs.201700526
  • Peer Reviewed / Open Access
• [Journal Article] Metamagnetism with TN = 97 K in a layered assembly of paddlewheel [Ru2] units and TCNQ: an empirical rule for interlayer distances determining the magnetic ground state (2018)
  • Author(s): Kosaka Wataru、Itoh Masahisa、Miyasaka Hitoshi
  • Journal Title: Materials Chemistry Frontiers Volume: 2 Issue: 3 Pages: 497-504
  • DOI: 10.1039/c7qm00534b
  • Peer Reviewed
• [Journal Article] Magnetic Switching by the In-Situ Electrochemical Control of Quasi-Spin-Peierls Singlet States in a Three-Dimensional Spin Lattice Incorporating TTF-TCNQ Salts (2018)
  • Author(s): Hiroki Fukunaga, Masanori Tonouchi, Kouji Taniguchi, Wataru Kosaka, Shojiro Kimura, Hitoshi Miyasaka
  • Journal Title: Chem. Eur. J. Volume: 24 Issue: 17 Pages: 4294-4303
  • DOI: 10.1002/chem.201704815
  • Peer Reviewed
• [Journal Article] Charge-Transfer Layered Assembly of a trans-Heteroleptic Paddlewheel-Type Diruthenium(II, II) Complex with a TCNQ Derivative: Electrochemical Tuning of the Magnetism (2018)
  • Author(s): Kouji Taniguchi, Nanami Shito, Hiroki Fukunaga, Hitoshi Miyasaka
  • Journal Title: Chem. Lett Volume: in press Issue: 5 Pages: 664-667
  • DOI: 10.1246/cl.180086
  • NAID: 130006732197
  • Peer Reviewed
• [Journal Article] Hammett-law Correlation in the Electron-donation Ability of trans-Heteroleptic Benzoate-bridged Paddlewheel-type Diruthenium(II,II) Complexes (2018)
  • Author(s): Sekine Yoshihiro、Aliyah Kinanti H.、Shimada Tomoka、Zhang Jun、Kosaka Wataru、Miyasaka Hitoshi
  • Journal Title: Chemistry Letters Volume: 47 Issue: 5 Pages: 693-696
  • DOI: 10.1246/cl.180155
  • NAID: 130006732223
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Magnetic Sponge Behavior via Electronic State Modulations (2018)
  • Author(s): Zhang Jun、Kosaka Wataru、Sugimoto Kunihisa、Miyasaka Hitoshi
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 16 Pages: 5644-5652
  • DOI: 10.1021/jacs.8b02428
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] One-Dimensional Chains of Paddlewheel-Type Dichromium(II,II) Tetraacetate Complexes: Study of Electronic Structure Influenced by σ- and π-Donation of Axial Linkers (2018)
  • Author(s): Huang Po-Jung、Natori Yoshiki、Kitagawa Yasutaka、Sekine Yoshihiro、Kosaka Wataru、Miyasaka Hitoshi
  • Journal Title: Inorganic Chemistry Volume: 57 Issue: 9 Pages: 5371-5379
  • DOI: 10.1021/acs.inorgchem.8b00352
  • Peer Reviewed
• [Journal Article] Layered ferrimagnets constructed from charge-transferred paddlewheel [Ru2] units and TCNQ derivatives: the importance of interlayer translational distance in determining magnetic ground state (2018)
  • Author(s): Kosaka Wataru、Liu Zhaoyuan、Miyasaka Hitoshi
  • Journal Title: Dalton Transactions Volume: 47 Issue: 34 Pages: 11760-11768
  • DOI: 10.1039/c8dt01566j
  • Peer Reviewed
• [Journal Article] Ionic Donor-Acceptor Chain Derived from an Electron-Transfer Reaction of a Paddlewheel-Type Diruthenium(II,?II) Complex and N,N′-Dicyanoquinonediimine (2018)
  • Author(s): Sekine Yoshihiro、Shimada Tomoka、Miyasaka Hitoshi
  • Journal Title: Chemistry - A European Journal Volume: 24 Issue: 50 Pages: 13093-13097
  • DOI: 10.1002/chem.201802630
  • Peer Reviewed
• [Journal Article] Thermally Induced Valence Tautomeric Transition in a Two-Dimensional Fe-Tetraoxolene Honeycomb Network (2018)
  • Author(s): Chen Jian、Sekine Yoshihiro、Komatsumaru Yuki、Hayami Shinya、Miyasaka Hitoshi
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 37 Pages: 12043-12047
  • DOI: 10.1002/anie.201807556
  • Peer Reviewed
• [Journal Article] Development of Ferromagnetic Fluctuations in Heavily Overdoped (Bi,Pb)2Sr2CuO6+δ Copper Oxides (2018)
  • Author(s): Kurashima Koshi、Adachi Tadashi、Suzuki Kensuke M.、Fukunaga Yasushi、Kawamata Takayuki、Noji Takashi、Miyasaka Hitoshi、Watanabe Isao、Miyazaki Masanori、Koda Akihiro、Kadono Ryosuke、Koike Yoji
  • Journal Title: Physical Review Letters Volume: 121 Issue: 5 Pages: 057002-057002
  • DOI: 10.1103/physrevlett.121.057002
  • Peer Reviewed
• [Journal Article] Gas-responsive porous magnet distinguishes the electron spin of molecular oxygen (2018)
  • Author(s): Kosaka Wataru、Liu Zhaoyuan、Zhang Jun、Sato Yohei、Hori Akihiro、Matsuda Ryotaro、Kitagawa Susumu、Miyasaka Hitoshi
  • Journal Title: Nature Communications Volume: 9 Issue: 1 Pages: 5420-5420
  • DOI: 10.1038/s41467-018-07889-1
  • NAID: 120006549327
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] In Situ Reversible Ionic Control for Non-Volatile Magnetic Phases in a Donor/Acceptor Metal-Organic Framework (2017)
  • Author(s): Kouji Taniguchi, Keisuke Narushima, Hajime Sagayama, Wataru Kosaka, Nanami Shito, Hitoshi Miyasaka
  • Journal Title: Advanced Functional Materials Volume: 27 Issue: 5 Pages: 1604990-1604990
  • DOI: 10.1002/adfm.201604990
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Slow relaxation of the magnetization observed in an antiferromagnetically ordered phase for SCM-based two-dimensional layered compounds (2017)
  • Author(s): Kagesawa Koichi, Nishimura Yuki, Yoshida Hiroki, Breedlove Brian K., Yamashita Masahiro, Miyasaka Hitoshi
  • Journal Title: Dalton Trans. Volume: 46 Issue: 10 Pages: 3170-3178
  • DOI: 10.1039/c6dt04636c
  • Peer Reviewed
• [Journal Article] Built-in TTF-TCNQ charge-transfer salts in p-stacked pillared layer frameworks (2017)
  • Author(s): Yoshihiro Sekine, Masanori Tonouchi, Taiga Yokoyama, Wataru Kosaka, Hitoshi Miyasaka
  • Journal Title: CrystEngComm Volume: 印刷中 Issue: 17 Pages: 2300-2304
  • DOI: 10.1039/c7ce00492c
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Magneto-ionic phase control in a quasi-layered donor/acceptor metal-organic framework by means of a Li-ion battery system (2017)
  • Author(s): K. Taniguchi, K. Narushima, K. Yamagishi, N. Shito, W. Kosaka, H. Miyasaka
  • Journal Title: Japanese Journal of Applied Physics Volume: 56 Issue: 6 Pages: 060307-060307
  • DOI: 10.7567/jjap.56.060307
  • NAID: 210000147818
  • Peer Reviewed
• [Journal Article] Ferromagnetic Exchange Coupling in a Family of MnIII Salen-Type Schiff-Base Out-of-Plane Dimers (2017)
  • Author(s): Kachi-Terajima Chihiro, Ishii Rikako, Tojo Yoshiaki, Fukuda Masato, Kitagawa Yasutaka, Asaoka Mizuki, Miyasaka Hitoshi
  • Journal Title: J. Phys. Chem. C Volume: 121 Issue: 22 Pages: 12454-12468
  • DOI: 10.1021/acs.jpcc.7b03336
  • Peer Reviewed
• [Journal Article] Three dimensional porous Hofmann clathrate [MIIPtII(CN)4] (M = Co, Ni) synthesized by using postsynthetic reductive elimination (2017)
  • Author(s): Takuro Okamura, Bin Wu, Hiroaki Iguchi, Brian K. Breedlove, Masahiro Yamashita, Wataru Kosaka, Hitoshi Miyasaka, Shinya Takaishi
  • Journal Title: ChemComm. Volume: 53 Issue: 48 Pages: 6512-6515
  • DOI: 10.1039/c7cc01766a
  • Peer Reviewed
• [Journal Article] Syntheses, Structures and Magnetic Properties of Tetranuclear Cubane-type and Heptanuclear Wheel-type Nickel(II) Complexes with 3-Methoxysalicylic Acid Derivatives (2017)
  • Author(s): F. Kobayashi, R. Ohtani, S. Teraoka, W. Kosaka, H. Miyasaka, Y. Zhang, L. F. Lindoy, S. Hayami, M. Nakamura
  • Journal Title: Dalton Trans. Volume: 46 Issue: 26 Pages: 8555-8561
  • DOI: 10.1039/c7dt01757j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] The Effect of Anion-Sublattice Structure on the Displacement Reaction in Copper Sulfide Cathodes of Rechargeable Magnesium Batteries (2017)
  • Author(s): Y. Tashiro, K. Taniguchi, H. Miyasaka
  • Journal Title: Chemistry Letters Volume: 46 Issue: 8 Pages: 1240-1242
  • DOI: 10.1246/cl.170503
  • NAID: 130005906969
  • Peer Reviewed
• [Journal Article] Gate-open-type Sorption in a Zigzag Paddlewheel Ru Dimer Chain Compound with a Phenylenediamine Linker Instructed by a Preliminary Structural Change of Desolvation (2017)
  • Author(s): Dou Changxiao, Kosaka Wataru, Miyasaka Hitoshi
  • Journal Title: Chem. Lett. Volume: 46 Issue: 9 Pages: 1288-1291
  • DOI: 10.1246/cl.170509
  • NAID: 130006067870
  • Peer Reviewed
• [Journal Article] Magnetic Phase Switching in a Tetraoxolene-Bridged Honeycomb Ferrimagnet Using a Lithium Ion Battery System (2017)
  • Author(s): K. Taniguchi, J. Chen, Y. Sekine, H. Miyasaka
  • Journal Title: Chemistry of Materials Volume: 29 Issue: 23 Pages: 10053-10059
  • DOI: 10.1021/acs.chemmater.7b03691
  • Peer Reviewed
• [Presentation] Guest-Sensitive Dynamical Magnets (2018)
  • Author(s): 宮坂等
  • Organizer: 日本化学会低次元系光機能材料研究会 第７回研究講演会「二次元構造を有するπ電子系の光・電子機能」
  • Invited
• [Presentation] Charge-Transfer Engineering for Porous Magnets (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: The 10th International Symposium on Nano and Supramolecular Chemistry (ISNSC10)
  • Int'l Joint Research / Invited
• [Presentation] Porous Magnets for Gas Sensing (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: 43rd International Conference on Coordination Chemistry (ICCC2018)
  • Int'l Joint Research / Invited
• [Presentation] Guest-Sensitive Dynamical Magnets (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: The 16th International Conference on Molecule-based Magnets (ICMM2018)
  • Int'l Joint Research / Invited
• [Presentation] Magnetic Switching in Redox-Active MOFs Using LIB (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: M3E.CL 2018 The Multifunctional Materials based on Strategic Metals
  • Int'l Joint Research / Invited
• [Presentation] Porous Magnets for Magnetoionics and Gas Sensing (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: 2018 Russia-Japan Joint Seminar “Non-equilibrium processing of materials: experiments and modeling”
  • Int'l Joint Research / Invited
• [Presentation] Porous Magnets for Gas Sensing (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: 146.SMS2018 (IMR)
  • Int'l Joint Research / Invited
• [Presentation] Dynamical pπ-dπ Figuration Tuned by Gas Accommodations (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: π-SYSTEM FIGURATION EUROPEAN-JAPANESE WORKSHOP 2018 (π-EJ 2018)
  • Int'l Joint Research / Invited
• [Presentation] Porous Magnets for Gas Sensing (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: 2018 Nankai International Symposium on Advanced Materials
  • Int'l Joint Research / Invited
• [Presentation] Porous Magnets for Gas Sensing (2018)
  • Author(s): Hitoshi Miyasaka
  • Organizer: Workshop on “Solid-State Electrochemistry for Coordination Complexes”
  • Int'l Joint Research / Invited
• [Presentation] Porous Molecular Magnets (2017)
  • Author(s): Hitoshi Miyasaka
  • Organizer: 6th Asian Conference on Coordination Chemistry (ACCC6)
  • Int'l Joint Research / Invited
• [Presentation] 変わる磁石”を創るー動的格子・空間制御による磁気スイッチングー (2017)
  • Author(s): 宮坂 等
  • Organizer: 関西学院大学 理学部講演会
  • Invited
• [Presentation] “変わる磁石”を創るー動的格子・空間制御による磁気スイッチングー (2017)
  • Author(s): 宮坂 等
  • Organizer: 低次元系光機能材料研究会 第6回サマーセミナー2017
  • Invited
• [Presentation] Porous Magnets for Magnetoionics and Gas Sensing (2017)
  • Author(s): Hitoshi Miyasaka
  • Organizer: 第2回錯体化学日米二国間会議
  • Int'l Joint Research / Invited
• [Presentation] Porous Magnets for Magnetoionics (2017)
  • Author(s): HITOSHI MIYASAKA
  • Organizer: 11th Japan-China Joint Symposium
  • Int'l Joint Research / Invited
• [Presentation] “変わる磁石”を創るー動的格子・空間制御による磁気スイッチングー (2017)
  • Author(s): 宮坂 等
  • Organizer: 138.名古屋大学 大学院理学研究科化学専攻講演会
  • Invited
• [Presentation] “変わる磁石”を創るー動的格子・空間制御による磁気スイッチングー (2017)
  • Author(s): 宮坂 等
  • Organizer: 139.筑波大学 大学院理学研究科化学専攻講演会
  • Invited
• [Book] 230.World Scientific Reference on Spin in Organics: Volume 4 -Spin in Organics, Materials and Energy Vol. 10 (2018)
  • Author(s): Hitoshi Miyasaka
  • Total Pages: 36
  • Publisher: World Scientific Pub. Co. Pte. Ltd.
  • ISBN: 9789813229075
• [Remarks] 宮坂研HP
  • URL: http://www.miyasaka-lab.imr.tohoku.ac.jp
• [Remarks] 宮坂研究室HP
  • URL: http://www.miyasaka-lab.imr.tohoku.ac.jp