複合機能性スピンクロスオーバー錯体における光誘起物性変換

• Project/Area Number: 17750048
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: University of Tsukuba
• Principal Investigator: 二瓶 雅之 University of Tsukuba, 大学院・数理物質科学研究科, 講師 (00359572)
• Project Period (FY): 2005 – 2007
• Project Status: Completed (Fiscal Year 2007)
• Budget Amount: ¥3,500,000 (Direct Cost: ¥3,500,000); Fiscal Year 2007: ¥1,000,000 (Direct Cost: ¥1,000,000); Fiscal Year 2006: ¥1,200,000 (Direct Cost: ¥1,200,000); Fiscal Year 2005: ¥1,300,000 (Direct Cost: ¥1,300,000)
• Keywords: スピンクロスオーバー錯体 / 光応答性分子 / 複合系 / 多重安定性

Research Abstract

鉄(II)スピンクロスオーバー(SC)錯体は、低スピン(LS)・高スピン(HS)状態を熱、光、圧力等の外場により可逆に変換可能なことから、分子スイッチとしての応用が期待される物質系である。しかしながら、SC錯体と他の物性を共存させることによる、複合系に関する研究例は未だに多くない。本研究では、分子性導体にSC錯体を導入することで伝導性一SC複合電子系を構築し、熱・光といった外場により電気伝導性を変換することを目的とした。具体的には、(1)鉄(II)SC錯体一分子性導体からなる複塩の合成、(2)TTF部位をもつSC錯体と分子性導体が連結された複合系の構築。まず、SC錯体カチオン([Fe(dppH)_2]^<2+>)とNi錯体アニオン([Ni(mnt)_2]^1)が1:2の組成をもつ複塩[Fe(dppH)_2][Ni(mnt)_2]_2 MeNO_2(1)を合成した。構造解析および磁化率測定から、錯体1は降温・昇温過程においてそれぞれ、高温相(200K↓)、低温相(140K↓)、準安定相(210K↑)の三つの相をもち、転位温度174Kにおいて鉄(II)イオンとNi錯体アニオンの相乗的構造・磁器相転位を観測した。一方、TTFドナー部位をもつ新規配位子dppTTFを用い[Fe(dppTTF)_2][Ni(mnt)_2]-2(BF_4)・PhCN(2)を合成した。2の温度依存磁化率および電気伝導度測定において、SCの構造・磁性変化と電気伝導性に明らかな相関が観測され、SCと電気伝導性との相乗的性が示唆された。

Research Products

• [Journal Article] Synthesis, structure and magnetic property of an iron(II) complex with nitronyl nitroxide groups (2007)
  • Author(s): Masayuki, Nihei, et. al.
  • Journal Title: Polyhedron 26 Pages: 1993-1996
  • Peer Reviewed
• [Journal Article] Magnetic Bistability and Single-Crystal-to-Single-Crystal Transformation Induced by Guest Desorption (2007)
  • Author(s): Masayuki, Nihei, et. al.
  • Journal Title: Journal of the American Chemical Society 129 Pages: 5312-5313
  • Peer Reviewed
• [Journal Article] Hetero-metal Mn-Cu and Mn-Ni Clusters with Tridentate Shiff-base Ligands (2007)
  • Author(s): Masayuki, Nihei, et. al.
  • Journal Title: Polyhedron 26 Pages: 1997-2007
  • Peer Reviewed
• [Journal Article] Manganese(III,IV)and Manganese(III)Oxide Clusters Traped by Copper(II)Complexes (2007)
  • Author(s): Masayuki, Nihei, et. al.
  • Journal Title: Inorganic Chemistry 46 Pages: 3810-3812
  • Peer Reviewed
• [Journal Article] Wheel-Shaped Single-Molecule Magnet of [MnII3MuIII4]:Quantum Tunneling of Magnetization under Static and Pulse Magnetic Fields (2007)
  • Author(s): Masayuki, Nihei, et. al.
  • Journal Title: Journal of the American Chemicla l Society 13 Pages: 8445-8453
  • Peer Reviewed
• [Journal Article] Spin Crossover Iron(III)Complexes (2007)
  • Author(s): Masayuki, Nihei, et. al.
  • Journal Title: Journal of the American Chemical Society 251 Pages: 2606-2621
  • Peer Reviewed
• [Journal Article] A Novel Octanuclear Manganese Cluster with [Mnu^<II>_4(μ_4-O)] Core (2006)
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Chemistry Letters 35 Pages: 440-441
• [Journal Article] A Dinuclear Single Molecule Magnet (2005)
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Chemistry Europian Journal 11 Pages: 843-849
• [Journal Article] Antiferromagnetic Fe^<III> Ring and Single-Molecule Magnet ]^<III> Wheel (2005)
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Inorganic Chemistry 44 Pages: 1208-1210
• [Journal Article] A Heterometal Single-Molecule Magnet of [Mn^<III> _2Ni^<II> _2Cl_2(salpa)_2] (2005)
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Journal of American Chemical Society 127 Pages: 4568-4569
• [Journal Article] Two-step Spin Conversion in a Cyanide-Bridged Ferrous Square (2005)
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Angewandte Chemie International Edition 44 Pages: 6484-6487
• [Journal Article] Rational Syntheses of Multi-nuclear High-spin complexes
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Bulletin of Japan Chemical Society (In press)
  • NAID: 10019937244
• [Journal Article] Synthesis, structure and magnetic property of an iron(II) complex with nitronyl nitroxide groups
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Polyhedron (In press)
• [Journal Article] Hetero-metal Mn-Cu and Mn-Ni Clusters with Tridentate Shiff-base Ligands
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Polyhedron (In press)
• [Journal Article] Magnetic Bistability and Single-Crystal-to-Single-Crystal Transformation Induced by Guest Desorption
  • Author(s): Masayuki Nihei et al.
  • Journal Title: Journal of the American Chemical Society (In press)
• [Presentation] シアン化物イオン架橋環状FeCO四核錯体における分子内電子移動 (2008)
  • Author(s): 二瓶雅之, 他
  • Organizer: 第88春季年会
  • Place of Presentation: 池袋
  • Year and Date: 2008-03-29
• [Presentation] Dual spin state conversion in an iron(II) complex (2008)
  • Author(s): Masayuki Nihei, et. al.
  • Organizer: 1st International Symposium on Interdisci plinary Materials Science
  • Place of Presentation: つくば
  • Year and Date: 2008-03-13
• [Presentation] A Multiple spin transition in an iron(II) complex (2007)
  • Author(s): Masayuki Nihei, et. al.
  • Organizer: 3rd International Symposium on Chemistry of Coordination Space
  • Place of Presentation: 淡路
  • Year and Date: 2007-12-10
• [Presentation] External Stimuli Rsponsive Metal cyanides (2007)
  • Author(s): Masayuki Nihei, et. al.
  • Organizer: The 1st International Symposium on Synergy of Elements
  • Place of Presentation: 大岡山
  • Year and Date: 2007-11-12
• [Presentation] シアン化物イオン架橋 8 核錯体の二次イオン電池正極材料への応用 (2007)
  • Author(s): 二瓶雅之, 他
  • Organizer: 第 55 回錯体化学討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2007-09-25
• [Presentation] External Stimuli-responsive Iron(II) Complexes with Multi-stability (2007)
  • Author(s): Masayuki Nihei, et. al.
  • Organizer: 1st Asian Conference on Coordination Chemistry
  • Place of Presentation: 岡崎
  • Year and Date: 2007-07-30