有機ラジカルを有するフラーレン誘導体を用いた磁性体の構築

• Project/Area Number: 09740476
• Research Category: Grant-in-Aid for Encouragement of Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Kyushu University
• Principal Investigator: 松田 建児 九州大学, 大学院工学研究科, 助手 (80262145)
• Project Period (FY): 1997 – 1998
• Project Status: Completed (Fiscal Year 1998)
• Budget Amount: ¥2,000,000 (Direct Cost: ¥2,000,000); Fiscal Year 1998: ¥900,000 (Direct Cost: ¥900,000); Fiscal Year 1997: ¥1,100,000 (Direct Cost: ¥1,100,000)
• Keywords: ニトロニルニトロキシド / フラーレン / メタノフラーレン / フリーラジカルの磁性

Research Abstract

ニトロニルニトロキシドラジカルを有するジフェニルジアゾメタンとC_<60>をトルエン中混合することにより、ニトロニルニトロキシドラジカルを有するメタノフラーレンを合成した。化合物はFAB MASSスペクトル((m+1)/z=1043),ESRスペクトル(5lines,g=2.01,a_N=7.5G),により同定した。UV-visスペクトルは短波長領域ではC_<60>と同じ吸収を示し,フラーレンの電子構造が変化していないことを示唆した。磁化率測定の結果,_XTの値より弱く反強磁性的に相互作用した孤立スピンが観測された。同様の方法で二分子付加体,ジラジカルの一分子,二分子付加体も得られた。CV測定では,フラーレンの一電子目の還元電位が-1.14V(vs.Fc/Fc^+on Pt)に現れ,ニトロニルニトロキシドに影響を与えることなくフラーレン部位にアニオンラジカルを発生させることができることを支持した。1分子付加体のX線結晶構造解析の結果,結晶はo-ジクロロベンゼンを1:1の割合で取り込んだ空間群P2,/cの結晶であり,ジフェニルジアゾメタン部位は[6,6]closedの形式で付加していることが明らかとなった。

Research Products

• [Publications] Kenji Matsuda: "Singlet and Triplet States Are Degenerate in 2,3-Dimethylenecyclohexane-1,4-diyl" J.Am.Chem.Soc.119(31). 7412-7413 (1997)
• [Publications] Kenji Matsuda: "Control of the “Superexchenge" Interaction through Diphenyl Sulfide 4,4-Diyl Magnetic Couplex by Changing the Oxidation State and Conformation of Sulfur Atom" J.Am.Chem.Soc.119(34). 8058-8064 (1997)
• [Publications] Kenji Matsuda: "Synthesis and ESR Characterization of Diphenylcarbenes Carrying t-Butyl Nitroxide and Nitronyl Nitroxide Radicals as Substituents and Having Quartet Ground States" Mol.Cryst.Liq.Cryst.306. 89-94 (1997)
• [Publications] Kenji Matsuda: "High-spin Organic Molecular Materials" Curr.Opin.Solid.State Mater.Sci.2(4). 446-450 (1997)
• [Publications] Kenji Matsuda: "Demonstration of the Degeneracy of the Singlet and Triplet States in 2,3-Dimethylenecyclohexane-1,4-diyl by Measurement of its Magnetic Properties" J.Chem.Soc.Perkin Trans.2. (5). 1023-1026 (1998)
• [Publications] Kenji Matsuda: "Design and Synthesis of Diphenyldiazomethanes Possessing Stable Aminoxyl Radicals:Photolytic Generation of Quartet Species and Their Reaction with C_<60>" J.Chem.Soc.Perkin Trans.2. (7). 1581-1588 (1998)
• [Publications] Kenji Matsuda: "Singlet and Triplet States Are Degenerate in 2,3-Dimethylenecyclohexane-1,4-diyl" J.Am.Chem.Soc.119(31). 7412-7413 (1997)
• [Publications] Kenji Matsuda: "Control of the “Superexchenge"Interaction through Diphenyl Sulfide 4,4-Diyl Magnetic Coupler by Changing the Oxidation State and Conformation of the Sulfur Atom" J.Am.Chem.Soc.119(34). 8058-8064 (1997)
• [Publications] Kenji Matsuda: "Synthesis and ESR Characterization of Diphenylcarbenes Carrying t-Butyl Nitroxide and Nitronyl Nitroxide Radicals as Substituents and Having Quartet Ground States" Mol.Cryst.Liq.Cryst.306. 89-94 (1997)
• [Publications] Kenji Matsuda: "High-spin Organic Molecular Materials" Curr.Opin.Solid.State Mater.Sci.2(4). 446-450 (1997)
• [Publications] Yoko Sano: "Formation of Ferromagnetic Chains by Photolysis of 1:1 Complexes of Bis(hexafluoroacetylacetonato)copper(II)with Diazodi(4-pyridyl)methane" J.Am.Chem.Soc.119(35). 8246-8252 (1997)
• [Publications] Ryuji Akabane: "Crystal Structures and Magnetic Properties of m-Phenylenebis(imidazole)Derivatives Having Two Nitronyl Nitroxide or Iminyl Nitroxide Rdaicals .The Two Kinds of Antiferromagnetic InterAction alternating along One-Dimensional Chains" J.Org.Chem.62(25). 8854-8861 (1997)