量子ナノワイヤー"単一次元鎖磁石"の証明と合理的設計法の開拓

• Project/Area Number: 14740386
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: 機能・物性・材料
• Research Institution: Tokyo Metropolitan University
• Principal Investigator: 宮坂 等 東京都立大学, 理学研究科, 助手 (50332937)
• Project Period (FY): 2002 – 2003
• Project Status: Completed (Fiscal Year 2003)
• Budget Amount: ¥3,300,000 (Direct Cost: ¥3,300,000); Fiscal Year 2003: ¥1,500,000 (Direct Cost: ¥1,500,000); Fiscal Year 2002: ¥1,800,000 (Direct Cost: ¥1,800,000)
• Keywords: 単一次元鎖磁石 / 量子磁石 / マンガン三価 / ニッケル二価

Research Abstract

1)Mn(III)salen誘導体である[Mn(saltmen)]+(saltmen2-=N,N'-(1,1,2,2-tetramethylethylene)bis(salicylideneiminate)dimerと[Ni(pao)2(L)2](pao-=2-pyridylaldoximate,L=unidentate ligand)との集積で得られる一連の[Mn2(saltmen)2Ni(pao)2(L)2](A)2を設計、合成した。このうち、L=pyridine, A=ClO4-に関しては最初の単一次元鎖磁石で、論文として発表し(J.Am.Chem.Soc.,2002,124,12837-12844、及び「化学」7月号)、そのシリーズとなる化合物群をInorg.Chem.に発表した。これらの発表は世界で最初の強磁性単一次元鎖磁石である。単一次元鎖磁石(Single-Chain Magnets)という名称も我々の論文で最初に発表されたものである。このような単一次元鎖磁石を系統的に作るために、本年度は原料錯体素子にNi(pao)2(bpy)やNi(pao)2(phen)を用い、Mn:Ni=2:1型の単一次元鎖磁石を見い出した。磁化緩和現象の評価を行い、スピン反転のエネルギー障壁がD=(8J+D)S2で表せることを見い出し、実測値との整合性を立証した。また、単一次元鎖磁石では初となる量子トンネル効果の可能性を見い出し発表した。
2)新しい単一次元鎖磁石の構築に成功し、Mn-Fe系、Mn-Cr系、Mn-Mn系のヘテロ金属一次元鎖を見い出し、その磁化緩和現象を確認した。
3)単一次元鎖磁石を構成するIsingスピンユニット錯体を合成し、その緩和現象と単一次元鎖磁石の緩和現象の相関を明らかにし、スピン緩和現象がユニット間の相互作用により連続的に評価できることを証明した。

Research Products

• [Publications] Masahiro Yamashita et al.: "Unprecedented Soliton Formation Mechanism in Quasi-One-Dimensional Chloro-Bridged PtII-PtIV Mixed-Valence Compound, {[Pt(en)2][PtCl2(en)2]}3(CuCl4)4・12H2O"Chem.Lett.. 32. 278-279 (2003)
• [Publications] Ryo Kanehama et al.: "Syntheses and physical properties of new charge-transfer salts consisting of a conducting BEDT-TTF column and magnetic 1D or 2D Fe(III) networks"Synth.Metals. 133-134. 553-554 (2003)
• [Publications] Hitoshi Miyasaka et al.: "A series of Ni(II) pyridyloximato (pao-) compounds [Ni(pao)2(L)2] (L = unidentate ligand) : as a coordination donor building block in the assembly with Mn(III) salen analogues"Synth.Metals. 137. 1245-1246 (2003)
• [Publications] Ryo Kanehama et al.: "New charge-transfer salts (ET)8(MnIIBr4)2(DCE)2 and (ET)3MnIIBr4 : Preparations, structures and physical properties (ET = BEDT-TTF, DCE = 1,2-dichloroethane)"Synth.Metals. 135-136. 633-634 (2003)
• [Publications] Takashi Ono et al.: "Tuning of spin density wave strength of Ni(III) complexes with strong electron-correlation"Synth.Metals. 135-136. 357-358 (2003)
• [Publications] Fumiyasu Iwahori et al.: "Platinum(II) Complex with S = 1/2 Organic Radical Ligand"Synth.Metals. 135-136. 355-356 (2003)
• [Publications] Hitoshi Miyasaka et al.: "Structure and Magnetic Properties of the Two-Dimensional Ferrimagnet, (NEt4)[{Mn(salen)}2Fe(CN)6] : Investigation of Magnetic Anisotropy on a Single Crystal"Inorg.Chem.. 42. 3509-3515 (2003)
• [Publications] Kazuya Nakata et al.: "Systematic Synthesis of Porphyrin Dimers Linked by Conjugated Oligoacetylene Bridges"Chem.Lett.. 32. 694-695 (2003)
• [Publications] Hitoshi Miyasaka et al.: "A Unique Diruthenium(II, III) Unit Surrounded by Tridentate Ligands of N-(2-Pyridyl)-2-oxy-5-chlorobenzylaminate"Inorg.Chem.Commun.. 6. 1078-1080 (2003)
• [Publications] Hitoshi Miyasaka et al.: "Heterometallic Hexanuclear Cluster with an S = 8 Spin Ground State : MnII{MnII(hfac)2}3{NiII(pao)3}2(hfac- = Hexafluoroacethylacetonate, pao- = Pyridine-2-aldoximate)"Inorg.Chem.. 42. 4501-4503 (2003)
• [Publications] Takayoshi Kuroda et al.: "Synthesis, crystal structure and magnetic properties of novel Mn12 single-molecule magnets with thiophenecarboxylate, [Mn12O12(O2CC4H3S)16(H2O)4], and its tetraphenylphosphonium salt"Polyhedron. 22. 1795-1801 (2003)
• [Publications] Masamichi Umemiya et al.: "Synthesis and Structural Determination of a Porphyrinatoplatinum(II) : meso-Tetrakis(4-t-butylphenyl)porphyrinatoplatinum(II)"Bull.Chem.Soc.Jpn. 76. 2123-2127 (2003)
• [Publications] Hitoshi Miyasaka et al.: "A Family of Diruthenium Compounds with Dianionic Tridentate Ligands of N-(2-pyridyl)-2-oxy-5-R-benzylaminate (R = H, Me, Cl, Br, NO2) : Isolation, Structure Determination and Electrochemistry"Inorg.Chem.. 42. 7683-7690 (2003)
• [Publications] Masahiro Yamashita et al.: "Carrier Doping Effect into Quasi-One-Dimensional Bromo-Bridged Ni(III) Complexes with Strong Electron-Correlation by Cu(II) Ions, [Ni1-xCux(chxn)2Br]Br2-x"Inorg.Chem.. 42. 7692-7694 (2003)
• [Publications] Hitoshi Miyasaka et al.: "[Mn2(saltmen)2Ni(pao)2(L)2](A)2 with L = pyridine, 4-picoline, 4-t-butylpyridine, N-methylimidazole and A = ClO4-, BF4-, PF6-, ReO4- : A Family of "Single-Chain Magnet""Inorg.Chem.. 42. 8203-8213 (2003)
• [Publications] Osamu Yamane et al.: "Pyrene-Fused Porphyrins : Annulation Reactions of meso-Pyrenylporphyrins"Chem.Lett.. 33. 40-41 (2003)
• [Publications] N.Kimura et al.: "13C NMR Spectra, 1H NMR Relaxation and ESR Measurements of Br2 Doped {[Pt(en)2][PtBr2(en)2]}3(CuBr4)4・12H2O"Synth.Metals. 135-136. 271-272 (2003)
• [Publications] 大川 尚, 伊藤 翼 編: "集積型金属錯体の科学 -物質機能の多様性を求めて-"化学同人. 10(273) (2003)
• [Publications] Hitoshi Miyasaka et al.: "Out-of-Plane Dimers of Mn(III) Quadridentate Schiff-Base Complexes with Saltmen2-and Naphtmen2-Ligands : Structure Analysis and Ferromagnetic Exchange"J. Chem. Soc., Dalton Trans.. 1528-1534 (2002)
• [Publications] Tomohiko Ishii et al.: "Cocrystallites Consisting of Metal Macrocycles with Fullerenes"Coord. Chem. Rev.. 226. 113-124 (2002)
• [Publications] H.Tanaka et al.: "Electron spin resonance studies of Co(tbp)-C60 single crystal"J. Phys. : Condens. Matter.. 14. 3993-4000 (2002)
• [Publications] M.Yamashita et al.: "Tuning of Electronic Structures of Quasi-One-Dimensional Bromo-Bridged Ni(II) Complexes with Strong Electron-Correlation by Doping of Co(III) Ions, [Ni1-xCox(Chxn)2Br]Br2"Inorg. Chem.. 41. 1998-2000 (2002)
• [Publications] C.Kachi-Terajima et al.: "Structure and electrochemistry of the bridging-ligand mono-substituted diruthenium compound, [Ru2II, III(O2CCH3)3(admpym)(Cl)(MeOH)](Hadmpym=2-amino-4,6-dimethyl-pyrimidine)"Inorg.Chimi.Acta. 332. 210-215 (2002)
• [Publications] H.Aso et al.: "Creations of Solitons and Polarons in MX-Chain Compounds, {[Pt(en)2][PtX2(en)2]}3(CuX4)4(X=Cl and Br)"Mol. Cryst. Liq. Cryst.. 376. 7-12 (2002)
• [Publications] Hitoshi Miyasaka et al.: "Out-of-plane Dimer Structures and Magnetic Properties of Mn(III) Quadridentate Schiff Base Compounds with N, N'-(1, 1, 2, 2-Tetramethylethylene)bis(5-chlorosalicylideneiminato)"Mol. Cryst. Liq. Cryst.. 379. 171-178 (2002)
• [Publications] Hitoshi Miyasaka et al.: "Reactions of Mn(III) Quadridentate Schiff Base Compounds with TCNQ Anion to Form Unusual TCNQ Derivatives by Alcoholysis"Mol. Cryst. Liq. Cryst.. 379. 197-204 (2002)
• [Publications] Toshio Manabe et al.: "Tuning of Spin Density Wave Strengths in Quasi-One-Dimensional Mixed-Halogen-Bridged Nickel(III) Complexes with Strong Electron Correlation, [NiIII(chxn)2Cll-xBrx](NO3)2"Inorg. Chem.. 41. 4993-4995 (2002)
• [Publications] Rodolphe Clerac et al.: "Evidence for 《Single Chain Magnet》 Behavior in a Heterometallic MnIII-NiII Chain"J. Am. Chem. Soc.. 124. 12837-12844 (2002)
• [Publications] 宮坂 等, 山下正廣: "一本の一次元金属錯体が磁石の性質を示すナノワーヤー単分子磁石ができた!・・・・室温単分子磁石を目指して"化学. 57. 12-16 (2002)
• [Publications] Naoko Aizawa et al.: "Syntheses and Physical Properties of Complexes of Fullerene with Magnetic Metal Porphyrins"Mol. Cryst. Liq. Cryst.. 376. 13-18 (2002)
• [Publications] Kouichi Takizawa et al.: "Crystal and Electronic Structures of Quasi-One-Dimensional Halogen-Bridged Binuclear Platinum Complexes, {(CnH2n+1)2NH2}4[Pt2(pop)4I](n=2-6)"Mol. Cryst. Liq. Cryst.. 376. 159-164 (2002)
• [Publications] Toshio Manabe et al.: "Physical Properties of Quasi-One-Dimensional Mixed-Metal-and Mixed-Halogen Complexes, Ni1-xPdx(chxn)2ClyBr1-yY2"Mol. Cryst. Liq. Cryst.. 376. 165-170 (2002)
• [Publications] Kazuya Nakata et al.: "Construction of a One-Dimensional Chain Composed of Mn6 Clusters and 4,4'-Bipyridine Linkers : The First Step for Creation of "Nano-Dots-Wires""Chem. Lett.. 7. 658-659 (2002)
• [Publications] Takayoshi Kuroda-Sowa et al.: "A Chemical Modification of a Mn12 Single-Molecule Magnet by Replacing Carboxylate Anions with Diphenylphosphate Anions"Chem. Lett.. 7. 682-683 (2002)
• [Publications] Kazuya Nakata et al.: "Synthesis, Structure and Magnetic Properties of the Antiferromagnetic Hexamanganese Cluster [Mn6(m4-O)2(O2CC6HF4)10(HO2CCH3)4]・(C7H8)"Mol. Cryst. Liq. Cryst.. 379. 211-216 (2002)