1999 Fiscal Year Annual Research Report

階段状π積層構造に基づいた新規超伝導相・磁性金属相の開発

Research Project

Project/Area Number	11304048
Research Category	Grant-in-Aid for Scientific Research (A)
Research Institution	Hokkaido University
Principal Investigator	稲辺保北海道大学, 大学院・理学研究科, 教授 (20168412)
Co-Investigator(Kenkyū-buntansha)	田島裕之東京大学, 物性研究所, 助教授 (60207032) 内藤俊雄北海道大学, 大学院・理学研究科, 講師 (20227713)
Keywords	フタロシアニン / 電子系の次元性 / 導電体 / 局在スピン / 電気伝導度 / 磁化率 / スピンラダー / Ni(dmit)_2
Research Abstract	中心金属がCO^<III>で、軸配位子としてCN基をもつフタロシアニン化合物を電解酸化すると多様な電子系の次元性を持つ導電性結晶が得られる。この次元性は結晶に取り込まれる溶媒や対イオンによって制御でき、多数の導電性中性ラジカル結晶や部分酸化塩結晶を得、その構造・物性研究を行なった。また、周期的に配置した磁気モーメントを含む導電体として、中心金属をFe^<III>で置換した一次元部分酸化導電体、TPP[Fe(Pc)(CN)_2]_2の作成にも成功した(TPP=tetraphenylphosphonium)。結晶構造は非磁性のCo^<III>の化合物と同形で、反射スペクトルや熱電能から求められるバンド幅も等しい。しかし、伝導度の温度依存性は全く異なり、Coの場合緩やかな半導体的挙動であるのに対して、Fe化合物では特に低温では急速な絶縁化が起こる。同様に磁化率の挙動も全く異なり、Coの場合温度依存の無いPauli常磁性であるのに対して、Fe化合物では局在スピンと伝導電子のスピンが全てCurie的な振舞いをする。さらに、20K付近に磁化率の極大が現われ、フタロシアニンのπ電子系を介在したd-π相互作用による反強磁性的な相互作用が働いていることが示された。この特異な半導体の電子及び磁気構造の詳細を調べるために、磁化率の異方性、低温ESRや磁気抵抗の測定を現在進めている。また、伝導電子源となるπラジカルを磁性源とした、Ni(dmit)_2アニオンを構成分子としたスピンラダーの構築にも成功した。同じ対イオンを非磁性アニオンであるAu(dmit)_2と組み合わせると一本鎖の構造にしかならないことから、ラジカルであるNi(dmit)_2の分子面を重ねた方向でのπ電子系の重なり積分によって梯子型構造の形成が促進することが明らかとなった。

Research Products
(14 results)

All Other

All Publications (14 results)

[Publications] 藤田安希子他: "Solid State Structures and Electrical Properties of Neutral Radical Crystals of Dicyano(phthalocyaninato)cobalt(III)"Journal of Porphyrins and Phthalocyanines. 3(8). 720-728 (1999)
[Publications] 藤縄佑他: "Unusual Electrical Properties of Neutral Mixed-Stack Charge-Transfer Complexes of DAP-BRL (DAP=1,6-Diaminopyrene, BRL=p-Bromanil)"Bulletin of the Chemical Society of Japan. 72(1). 21-26 (1999)
[Publications] 内藤俊雄他: "Preparation of a New Conducting and Magnetic Material Based on Coordination Compounds"Synthetic Matals. 102. 1687-1688 (1999)
[Publications] 芥川智行他: "Ion Cavities within NH_4^+(Crown Ether)[Ni(dmit)_2] Salts"Synthetic Metals. 102. 1747-1748 (1999)
[Publications] 松田真生他: "Phthalocyanine Molecular Conductors with Paramagnetic Iron(III)"Synthetic Metals. 102. 1774-1775 (1999)
[Publications] 今井宏之他: "M(dmit)_2 Salts with Nitronyl Nitroxide Radical Cations. Non-Magnetic Single-Chain Formation vs. Antiferromagnetic Spin-Ladder-Chain Formation of M(dmit)_2"Journal of the American Chemical Society. 121(35). 8098-8103 (1999)
[Publications] 伊藤英輔他: "Tautomeric Structure of N-Salicylideneaniline Derivatives Studied by Soft X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy"Journal of Synchrotron Radiation. 6. 781-783 (1999)
[Publications] 大塚岳夫他: "Impurity doping to molecular spin-ladders : Magnetic properties of p-EPYNN^+・[Ni(dmit)_2]^-_<1-x>[Au(dmit)_2]^-_x"Synthetic Metals. 103. 2292-2293 (1999)
[Publications] 阿波賀邦夫他: "Magnetic Properties of Molecular Compounds of Mn_<12>Ph"Molecular Crystals and Liquid Crystals. 335. 473-482 (1999)
[Publications] 芥川智行他: "Crystal Structures and Optical Properties of Cation Radical Salts of a Tetrathiafulvalene Trisannulated Macrocycle"Juurnal of Materials Chemistry. 9(11). 2737-2742 (1999)
[Publications] 阿波賀邦夫他: "Unusual Crystal Structures and Properties of Nitronylnitroxide radicals. Possible RVB States in Molecule-Based Magnets"Phil. Trans. R. Soc. Lond. A. 357. 2893-2922 (1999)
[Publications] 芥川智行他: "Tuning of Intramolecular π-π Overlap Mode of Tetrathiafulvalene Bisannulated Macrocycles in the Open-Shell Electronic State"Chemistry Letters. (1). 132-133 (2000)
[Publications] 亀屋めぐみ他: "Rubrene Cation Radical Stabilized by Polyiodide Chains in the (Rubrene)I_9 Crystal"Bulletin of the Chemical Society of Japan. 73(1). 61-65 (2000)
[Publications] 松田真生他: "A one-dimensional macrocyclic π-ligand conductor carrying the magnetic center. Structure and electrical, optical and magnetic properties of TPP[Fe(Pc)(CN)_2]_2"Journal of Materials Chemistry. 10(3). 631-636 (2000)

1999 Fiscal Year Annual Research Report

階段状π積層構造に基づいた新規超伝導相・磁性金属相の開発

Principal Investigator

稲辺 保 北海道大学, 大学院・理学研究科, 教授 (20168412)

Research Products

[Publications] 藤田安希子 他: "Solid State Structures and Electrical Properties of Neutral Radical Crystals of Dicyano(phthalocyaninato)cobalt(III)"Journal of Porphyrins and Phthalocyanines. 3(8). 720-728 (1999)

[Publications] 藤縄 佑 他: "Unusual Electrical Properties of Neutral Mixed-Stack Charge-Transfer Complexes of DAP-BRL (DAP=1,6-Diaminopyrene, BRL=p-Bromanil)"Bulletin of the Chemical Society of Japan. 72(1). 21-26 (1999)

[Publications] 内藤俊雄 他: "Preparation of a New Conducting and Magnetic Material Based on Coordination Compounds"Synthetic Matals. 102. 1687-1688 (1999)

[Publications] 芥川智行 他: "Ion Cavities within NH_4^+(Crown Ether)[Ni(dmit)_2] Salts"Synthetic Metals. 102. 1747-1748 (1999)

[Publications] 松田真生 他: "Phthalocyanine Molecular Conductors with Paramagnetic Iron(III)"Synthetic Metals. 102. 1774-1775 (1999)

[Publications] 今井宏之 他: "M(dmit)_2 Salts with Nitronyl Nitroxide Radical Cations. Non-Magnetic Single-Chain Formation vs. Antiferromagnetic Spin-Ladder-Chain Formation of M(dmit)_2"Journal of the American Chemical Society. 121(35). 8098-8103 (1999)

[Publications] 伊藤 英輔 他: "Tautomeric Structure of N-Salicylideneaniline Derivatives Studied by Soft X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy"Journal of Synchrotron Radiation. 6. 781-783 (1999)

[Publications] 大塚岳夫 他: "Impurity doping to molecular spin-ladders : Magnetic properties of p-EPYNN^+・[Ni(dmit)_2]^-_<1-x>[Au(dmit)_2]^-_x"Synthetic Metals. 103. 2292-2293 (1999)

[Publications] 阿波賀邦夫 他: "Magnetic Properties of Molecular Compounds of Mn_<12>Ph"Molecular Crystals and Liquid Crystals. 335. 473-482 (1999)

[Publications] 芥川智行 他: "Crystal Structures and Optical Properties of Cation Radical Salts of a Tetrathiafulvalene Trisannulated Macrocycle"Juurnal of Materials Chemistry. 9(11). 2737-2742 (1999)

[Publications] 阿波賀邦夫 他: "Unusual Crystal Structures and Properties of Nitronylnitroxide radicals. Possible RVB States in Molecule-Based Magnets"Phil. Trans. R. Soc. Lond. A. 357. 2893-2922 (1999)

[Publications] 芥川智行 他: "Tuning of Intramolecular π-π Overlap Mode of Tetrathiafulvalene Bisannulated Macrocycles in the Open-Shell Electronic State"Chemistry Letters. (1). 132-133 (2000)

[Publications] 亀屋 めぐみ 他: "Rubrene Cation Radical Stabilized by Polyiodide Chains in the (Rubrene)I_9 Crystal"Bulletin of the Chemical Society of Japan. 73(1). 61-65 (2000)

[Publications] 松田真生 他: "A one-dimensional macrocyclic π-ligand conductor carrying the magnetic center. Structure and electrical, optical and magnetic properties of TPP[Fe(Pc)(CN)_2]_2"Journal of Materials Chemistry. 10(3). 631-636 (2000)

稲辺保北海道大学, 大学院・理学研究科, 教授 (20168412)

[Publications] 藤田安希子他: "Solid State Structures and Electrical Properties of Neutral Radical Crystals of Dicyano(phthalocyaninato)cobalt(III)"Journal of Porphyrins and Phthalocyanines. 3(8). 720-728 (1999)

[Publications] 藤縄佑他: "Unusual Electrical Properties of Neutral Mixed-Stack Charge-Transfer Complexes of DAP-BRL (DAP=1,6-Diaminopyrene, BRL=p-Bromanil)"Bulletin of the Chemical Society of Japan. 72(1). 21-26 (1999)

[Publications] 内藤俊雄他: "Preparation of a New Conducting and Magnetic Material Based on Coordination Compounds"Synthetic Matals. 102. 1687-1688 (1999)

[Publications] 芥川智行他: "Ion Cavities within NH_4^+(Crown Ether)[Ni(dmit)_2] Salts"Synthetic Metals. 102. 1747-1748 (1999)

[Publications] 松田真生他: "Phthalocyanine Molecular Conductors with Paramagnetic Iron(III)"Synthetic Metals. 102. 1774-1775 (1999)

[Publications] 今井宏之他: "M(dmit)_2 Salts with Nitronyl Nitroxide Radical Cations. Non-Magnetic Single-Chain Formation vs. Antiferromagnetic Spin-Ladder-Chain Formation of M(dmit)_2"Journal of the American Chemical Society. 121(35). 8098-8103 (1999)

[Publications] 伊藤英輔他: "Tautomeric Structure of N-Salicylideneaniline Derivatives Studied by Soft X-ray Absorption Spectroscopy and X-ray Photoelectron Spectroscopy"Journal of Synchrotron Radiation. 6. 781-783 (1999)

[Publications] 大塚岳夫他: "Impurity doping to molecular spin-ladders : Magnetic properties of p-EPYNN^+・[Ni(dmit)_2]^-_<1-x>[Au(dmit)_2]^-_x"Synthetic Metals. 103. 2292-2293 (1999)

[Publications] 阿波賀邦夫他: "Magnetic Properties of Molecular Compounds of Mn_<12>Ph"Molecular Crystals and Liquid Crystals. 335. 473-482 (1999)

[Publications] 芥川智行他: "Crystal Structures and Optical Properties of Cation Radical Salts of a Tetrathiafulvalene Trisannulated Macrocycle"Juurnal of Materials Chemistry. 9(11). 2737-2742 (1999)

[Publications] 阿波賀邦夫他: "Unusual Crystal Structures and Properties of Nitronylnitroxide radicals. Possible RVB States in Molecule-Based Magnets"Phil. Trans. R. Soc. Lond. A. 357. 2893-2922 (1999)

[Publications] 芥川智行他: "Tuning of Intramolecular π-π Overlap Mode of Tetrathiafulvalene Bisannulated Macrocycles in the Open-Shell Electronic State"Chemistry Letters. (1). 132-133 (2000)

[Publications] 亀屋めぐみ他: "Rubrene Cation Radical Stabilized by Polyiodide Chains in the (Rubrene)I_9 Crystal"Bulletin of the Chemical Society of Japan. 73(1). 61-65 (2000)

[Publications] 松田真生他: "A one-dimensional macrocyclic π-ligand conductor carrying the magnetic center. Structure and electrical, optical and magnetic properties of TPP[Fe(Pc)(CN)_2]_2"Journal of Materials Chemistry. 10(3). 631-636 (2000)