2001 Fiscal Year Annual Research Report

π共役系配位子錯体の積層構造制御により構築される磁性導電体の研究

Research Project

Project/Area Number	11224201
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)	中村貴義北海道大学, 電子科学研究所, 教授 (60270790) 内藤俊雄北海道大学, 大学院・理学研究科, 助教授 (20227713)
Keywords	フタロシアニン / 巨大な負の磁気抵抗 / 部分酸化塩 / 電子スピン共鳴 / 強相関電子系 / スピンラダー / ドーピング / 圧力依存性
Research Abstract	13年度の成果は以下の通りである。・フタロシアニン(Pc)系:軸配位子を導入した一次元導電体であるTPP[Fe^<III>(Pc)(CN)_2]_2の巨大な負の磁気抵抗が見いだされ、その大きな異方性と、磁化率の異方性との相関から、特異なπ-d相互作用が働いていることが示唆されていたが、その起源はまだ明確になっていなかった。部分酸化塩のESR信号は検知することができなかったが、単純塩及びそのCo(III)との固溶体を用いることで、Fe(III)の信号の検知に成功し、そのg因子が非常に大きな異方性を持つことが初めて明らかになった。従って、磁気モーメントの大きな方向に外部磁場が印加されたとき、磁気モーメントの整列が顕著になり、伝導電子のスピン散乱が押さえられ、負の磁気抵抗が現れると解釈できる。この研究と平行して、π電子系の拡張についても検討し、ナフタロシアニン(Nc)系を取り上げた。異性体の分離が必要な1,2-Ncについては、単離法を開発し、軸配位子をもつCo(III)錯体の部分酸化塩の開発に成功した。また、2,3-Ncについては導電性の中性ラジカル結晶を得、その電気伝導度の圧力依存性を調べた。両系ともクーロン反発効果が物性に大きく影響することが明らかとなった。・Ni(dmit)_2及びET系:スピンラダー構造となる新たなNi(dmit)_2塩を見いだした。また、この系へのドーピングの可能性を調べるために水素結合型カチオンとの塩を合成し、カチオンがある構造で配列したときプロトン欠陥が生じ、電気伝導度が著しく向上することが明らかとなった。また、ET系に局在磁気モーメントを導入した新規導電性結晶を作成し、その電気物性が圧力により非常に敏感に変化することを明らかにした。

Research Products

(26 results)

All Other

All Publications (26 results)

[Publications] 稲辺保: "Novel Phthalocyanine-based Conductors : Tunable π-π Stacking Structure Through the Steric and Chemical Interactions of Axial Ligands"Journal of Porphyrins and Phthalocyanines. 5. 3-12 (2001)
[Publications] 浅利剛裕, 他: "Charge-Transfer Complexes of PXX (PXX=6,12-Dioxaanthanthrene). The Formal Charge and Molecular Geometry"Bulletin of the Chemistry Society of Japan. 74. 53-58 (2001)
[Publications] 芥川智行, 他: "Diversity in the 1/2 Spin Arrangement of [Ni(dmit)_2]^-Anions in Divalent Ca^<2+> (crown ether) Supramolecular Cation Salts"Journal of Materials Chemistry. 11. 2118-2124 (2001)
[Publications] 芥川智行, 他: "Ionic Channel Structures in [(M^+)_x([18]crown-6)][Ni(dmit)_2]_2 Molecular Conductors"Chemistry A European Journal. 7. 4902-4912 (2001)
[Publications] E.H.Gacho, 他: "Isolation and Structural and Optical Characterization of the C_<2v> 1,2-Naphthalocyanine Isomer"Chemistry Letters. 260-261 (2001)
[Publications] 花咲徳亮, 他: "Giant Negative Magnetoresistance of One-Dimensional Conductor TPP[Fe(Pc)(CN)_2]_2"Synthetic Metals. 120. 797-798 (2001)
[Publications] 小林典仁, 他: "Synthesis, Electrical Properties of a Novel Ni-dithiolene Complex with Dimerized Structure"Synthetic Metals. 120. 1055-1056 (2001)
[Publications] 松田真生, 他: "Structure and Electrical and Magnetic Properties of (PTMA)_x[M(Pc)(CN)_2]・(solvent)(PTMA=phenyltrimethylammonium and [M(Pc)(CN)_2]=dicyano(phthalocyaninato)M^<III> with M=Co and Fe). Partial Oxidation by Partial Solvent Occupation of the Cationic Site"Journal of Materials Chemistry. 11. 2493-2497 (2001)
[Publications] 内藤俊雄, 他: "Peculiar Physical Properties of (ET)_3(MnCl_4)(TCE)"Synthetic Metals. 120. 877-878 (2001)
[Publications] 内藤俊雄, 他: "A New Molecular Metal Based on Pd(dmit)_2 : Synthesis, Structure and Electrical Properties of (C_7H_<13>NH)(Pd(dmit)_2]_2 (dmit^<2->=2-thioxo-1,3-dithiole-4,5-dithiolate)"Journal of Materials Chemistry. 11. 2199-2204 (2001)
[Publications] 内藤俊雄, 他: "β"-(ET)_3(MnCl_4)(1,1,2-C_2H_3Cl_3)(ET=bis(ethylenedithio)tetrathiafulvalene) ; a Pressure-sensitive New Molecular Conductor with Localized Spins"Journal of Materials Chemistry. 11. 2221-2227 (2001)
[Publications] 大塚岳夫, 他: "Magnetic Conversion Induced by Non-Magnetic Impurities in a Molecular Spin Ladder System, p-EPYNN・[Ni(dmit)_2]"Journal of Physical Society of Japan. 70. 2711-2716 (2001)
[Publications] 長谷川達生, 他: "Neutral-Ionic Phase Transition of (BEDT-TTF)(ClMeTCNQ) under Pressure"Physical Review B. 64. 5106 (2001)
[Publications] 武田啓司, 他: "Magnetic Anisotropy, Tunneling Effects, High-frequency EPR and Molecular Structure of Fast Relaxation Species of Mn_<12>"Physical Review B. 65. 4424 (2002)
[Publications] 中村貴義, 他: "Conducting Langmuir-Blodgett Films of Bis[bis(methylthio)tetrathiafulvalenedithiolate]-gold Complex"Chemistry Letters. 134-135 (2001)
[Publications] S.Mikami, 他: "Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [Fe^<III>(TPP)]^+[TCNE]^-"Journal of Chemical Society Dalton Transactions. 448-455 (2001)
[Publications] L.Cronin, 他: "Unique Structural Topologies Involving Metal-Metal and Metal-Sulphur Interactions : Salts of [Ni(dmit)_2]^<X-> with cis-anti-cis-dicyclohexyl-18-crown-6 Complexed Counterions"Journal of Chemical Society Dalton Transactions. 1347-1351 (2001)
[Publications] K.Sakai, 他: "Partially-Oxidized Ni(dmit)_2 Salt with Copper Ions"Synthetic Metals. 805-806 (2001)
[Publications] 長谷川達生, 他: "Donor-Acceptor Type Complexes of (BEDT-TTF)(TCNQ) Analogues : Peculiar Magnetic Transistion in (BEDO-TTF)(Cl_2TCNQ)"Synthetic Metals. 120. 991-992 (2001)
[Publications] S.Nishihara, 他: "[Ni(dmit)_2]^-Salts of a Supramolecular Cation, Sc^+(12-crown-4)_2"Synthetic Metals. 121. 1806-1807 (2001)
[Publications] T.Takahashi, 他: "Structure and Electronic Properties of Bis[bis(methylthio) tetrathiafulvalenedithiolate)-Gold(III) Langmuir-Blodgett Films"Thin Solid Films. 393. 7-11 (2001)
[Publications] K.Shitagami, 他: "Potassium Bis(4,5-dimercapo-1,3-dithiole-2-thionato)nickelate (1,4,7,10,13,16-hexaoxa-2,3:11,12-dibenzocyclooctadeca-2, 11-diene) Propanone Solvate"Acta Crystallographica Section C. 57. 1271-1273 (2001)
[Publications] K.Shitagami, 他: "An Infinite Supramolecular Array Structure in Metal Dithiolate Complexes : Crystal Structure of K(Dibenzo-18-crown-6)[M(dmit)_2](CH_3CN)_2(M : Ni, Au)"Cryst. Eng. Commun.. 52 (2001)
[Publications] S.Nishihara, 他: "Formation of Molecular Spin Ladder Induced by Supramolecular Cation Structure"Chemical Communication. 408-409 (2002)
[Publications] 芥川智行, 他: "Crystal Structures and Magnetism of [Ni(dmit)_2]^-Salts with Supramolecular Cations of M^+(15-crown-5)"Molecular Crystals and Liquid Crystals. (印刷中).
[Publications] 芥川智行, 他: "Formation of Oriented Molecular Nanowires on Mica Surface"Proc.Natl.Acad.Sci.USA. (印刷中).

2001 Fiscal Year Annual Research Report

π共役系配位子錯体の積層構造制御により構築される磁性導電体の研究

Principal Investigator

稲辺 保 北海道大学, 大学院・理学研究科, 教授 (20168412)

Research Products

[Publications] 稲辺 保: "Novel Phthalocyanine-based Conductors : Tunable π-π Stacking Structure Through the Steric and Chemical Interactions of Axial Ligands"Journal of Porphyrins and Phthalocyanines. 5. 3-12 (2001)

[Publications] 浅利剛裕, 他: "Charge-Transfer Complexes of PXX (PXX=6,12-Dioxaanthanthrene). The Formal Charge and Molecular Geometry"Bulletin of the Chemistry Society of Japan. 74. 53-58 (2001)

[Publications] 芥川智行, 他: "Diversity in the 1/2 Spin Arrangement of [Ni(dmit)_2]^-Anions in Divalent Ca^<2+> (crown ether) Supramolecular Cation Salts"Journal of Materials Chemistry. 11. 2118-2124 (2001)

[Publications] 芥川智行, 他: "Ionic Channel Structures in [(M^+)_x([18]crown-6)][Ni(dmit)_2]_2 Molecular Conductors"Chemistry A European Journal. 7. 4902-4912 (2001)

[Publications] E.H.Gacho, 他: "Isolation and Structural and Optical Characterization of the C_<2v> 1,2-Naphthalocyanine Isomer"Chemistry Letters. 260-261 (2001)

[Publications] 花咲徳亮, 他: "Giant Negative Magnetoresistance of One-Dimensional Conductor TPP[Fe(Pc)(CN)_2]_2"Synthetic Metals. 120. 797-798 (2001)

[Publications] 小林典仁, 他: "Synthesis, Electrical Properties of a Novel Ni-dithiolene Complex with Dimerized Structure"Synthetic Metals. 120. 1055-1056 (2001)

[Publications] 内藤俊雄, 他: "Peculiar Physical Properties of (ET)_3(MnCl_4)(TCE)"Synthetic Metals. 120. 877-878 (2001)

[Publications] 内藤俊雄, 他: "A New Molecular Metal Based on Pd(dmit)_2 : Synthesis, Structure and Electrical Properties of (C_7H_<13>NH)(Pd(dmit)_2]_2 (dmit^<2->=2-thioxo-1,3-dithiole-4,5-dithiolate)"Journal of Materials Chemistry. 11. 2199-2204 (2001)

[Publications] 内藤俊雄, 他: "β"-(ET)_3(MnCl_4)(1,1,2-C_2H_3Cl_3)(ET=bis(ethylenedithio)tetrathiafulvalene) ; a Pressure-sensitive New Molecular Conductor with Localized Spins"Journal of Materials Chemistry. 11. 2221-2227 (2001)

[Publications] 大塚岳夫, 他: "Magnetic Conversion Induced by Non-Magnetic Impurities in a Molecular Spin Ladder System, p-EPYNN・[Ni(dmit)_2]"Journal of Physical Society of Japan. 70. 2711-2716 (2001)

[Publications] 長谷川達生, 他: "Neutral-Ionic Phase Transition of (BEDT-TTF)(ClMeTCNQ) under Pressure"Physical Review B. 64. 5106 (2001)

[Publications] 武田啓司, 他: "Magnetic Anisotropy, Tunneling Effects, High-frequency EPR and Molecular Structure of Fast Relaxation Species of Mn_<12>"Physical Review B. 65. 4424 (2002)

[Publications] 中村貴義, 他: "Conducting Langmuir-Blodgett Films of Bis[bis(methylthio)tetrathiafulvalenedithiolate]-gold Complex"Chemistry Letters. 134-135 (2001)

[Publications] S.Mikami, 他: "Structure, optical and magnetic behaviour of meso-tetraphenylporphyrinatoiron(III) tetracyanoethenide, [Fe^<III>(TPP)]^+[TCNE]^-"Journal of Chemical Society Dalton Transactions. 448-455 (2001)

[Publications] L.Cronin, 他: "Unique Structural Topologies Involving Metal-Metal and Metal-Sulphur Interactions : Salts of [Ni(dmit)_2]^<X-> with cis-anti-cis-dicyclohexyl-18-crown-6 Complexed Counterions"Journal of Chemical Society Dalton Transactions. 1347-1351 (2001)

[Publications] K.Sakai, 他: "Partially-Oxidized Ni(dmit)_2 Salt with Copper Ions"Synthetic Metals. 805-806 (2001)

[Publications] 長谷川達生, 他: "Donor-Acceptor Type Complexes of (BEDT-TTF)(TCNQ) Analogues : Peculiar Magnetic Transistion in (BEDO-TTF)(Cl_2TCNQ)"Synthetic Metals. 120. 991-992 (2001)

[Publications] S.Nishihara, 他: "[Ni(dmit)_2]^-Salts of a Supramolecular Cation, Sc^+(12-crown-4)_2"Synthetic Metals. 121. 1806-1807 (2001)

[Publications] T.Takahashi, 他: "Structure and Electronic Properties of Bis[bis(methylthio) tetrathiafulvalenedithiolate)-Gold(III) Langmuir-Blodgett Films"Thin Solid Films. 393. 7-11 (2001)

[Publications] K.Shitagami, 他: "Potassium Bis(4,5-dimercapo-1,3-dithiole-2-thionato)nickelate (1,4,7,10,13,16-hexaoxa-2,3:11,12-dibenzocyclooctadeca-2, 11-diene) Propanone Solvate"Acta Crystallographica Section C. 57. 1271-1273 (2001)

[Publications] K.Shitagami, 他: "An Infinite Supramolecular Array Structure in Metal Dithiolate Complexes : Crystal Structure of K(Dibenzo-18-crown-6)[M(dmit)_2](CH_3CN)_2(M : Ni, Au)"Cryst. Eng. Commun.. 52 (2001)

[Publications] S.Nishihara, 他: "Formation of Molecular Spin Ladder Induced by Supramolecular Cation Structure"Chemical Communication. 408-409 (2002)

[Publications] 芥川智行, 他: "Crystal Structures and Magnetism of [Ni(dmit)_2]^-Salts with Supramolecular Cations of M^+(15-crown-5)"Molecular Crystals and Liquid Crystals. (印刷中).

[Publications] 芥川智行, 他: "Formation of Oriented Molecular Nanowires on Mica Surface"Proc.Natl.Acad.Sci.USA. (印刷中).

稲辺保北海道大学, 大学院・理学研究科, 教授 (20168412)

[Publications] 稲辺保: "Novel Phthalocyanine-based Conductors : Tunable π-π Stacking Structure Through the Steric and Chemical Interactions of Axial Ligands"Journal of Porphyrins and Phthalocyanines. 5. 3-12 (2001)