2000 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, 講師 (20227713)
Keywords	局在スピン / 一次元伝導体 / フタロシアニン / 電気伝導度 / π-d系 / スピンラダー / Ni(dmit)_2 / 負の磁気抵抗
Research Abstract	周期的に配置した磁気モーメントを含む導電体の作成として、中心金属がFe^<III>で、軸配位子としてCN基をもつフタロシアニン化合物と種々のカチオンとの組み合わせについて検討した。その結果、既に得られているTPP(=tetrphenylphosphonium)塩に加え、PTMA(=phenyltrimethylammonium)や有機ドナーPXX(=6,12-dioxaanthanthrene)をカチオン成分とする部分酸化塩結晶が得られた。これらの結晶構造は全て中心金属がCo^<III>も得られ、またそれらはFe^<III>塩と同形である。高温部の熱電能の温度変化もまた、Co^<III>塩とFe^<III>塩で共通で、フタロシアニンπ電子系から成るバンド構造が等しいことを反映している。一方、伝導度の温度変化は中心金属によって大きく異なる。非磁性のCo^<III>の場合、高温部で金属的な挙動が見られ、温度低下で緩やかな半導体的な挙動となるが、磁気モーメントを持つFe^<III>の場合、低温部でさらに急激な比抵抗の増大が必ず起こる。この低温部で起こるFe^<III>塩の特徴的な伝導キャリアの散乱は外部磁場によって押さえられることを見い出し、これが巨大な負の磁気抵抗として観測されることを発表した。電子系が一次元性である物質の負の磁気抵抗は非常にめずらしいものである。また、Fe^<III>塩の磁化率は大きな異方性を示し、この異方性に対応する形で負の磁気抵抗が現れることから、Fe^<III>塩が新規π-d系物質であることが明らかとなった。この負の磁気抵抗の機構については、まだ不明な点が多く、角度依存性等の実験によってさらに詳細について調べる予定である。上記の研究とは独立に、πラジカルを磁性源とするNi(dmit)_2塩の構造・物性研究を行い、新たにスピンラダー構造をもつ塩や、二量体-スピンラダー転移を示す塩が見い出された。さらにスピンラダーへのドーピングの可能性を水素結合系カチオンを用いて調べている。

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] 高松信博他: "One-Dimensional Antiferromagnetic Chain in [Ni(dmit)_2]^- Salts of [K^+ or Rb^+ (4,13-diaza-18-crown-6)] Supramolecular Cation"Inorganic Chemistry. 39(5). 870-871 (2000)
[Publications] 芥川智行他: "M^+ (12-crown-4) Supramolecular Cations (M^+=Na^+,K^+,Rb^+,and NH_4^+) within Ni (2-thioxo-1,3-dithiole-4,5-dithiolate)_2 Molecular Conductor"Inorganic Chemistry. 39(12). 2645-2651 (2000)
[Publications] 芥川智行他: "Co^<2+> (15-crown-5) Magnetic Supramolecular Cation in [Ni(dmit)_2]^-π-Spin System"The Journal of Physical Chemistry B. 104(25). 5871-5873 (2000)
[Publications] 花咲徳亮他: "Giant Negative Magnetoresistance in One- Dimensional π-d System : TPP[Fe(Pc)(CN)_2]_2(TPP=tetraphenylphosphonium,Pc=phthalocyanine)"Molecular Crystals and Liquid Crystals. 343. 41-46 (2000)
[Publications] 高松信博他: "M^+(Crown Ether) Supramolecular Cations (M^+=K^+, Rb^+, NH_4^+) for Controlling Magnetic Properties of Monovalent [Ni(dmit)_2] Salts"Molecular Crystals and Liquid Crystals. 343. 163-168 (2000)
[Publications] 花咲徳亮他: "Giant Negative Magnetoresistance in Quasi-One-Dimensional Conductor TPP[Fe(Pc)(CN)_2]_2 : Interplay between Local Moments and One-Dimensional Conduction Electrons"Physical Review B. 62(9). 5839-5842 (2000)
[Publications] 松村直子他: "Multi-Dimensional π-π Stacking Interaction in Neutral Radical Crystals Obtained by Electrochemical Oxidation of [Co^<III>(2,3-Nc)(CN)_2]^- (2,3-Nc=2,3-naphthalocyanine)"Journal Materials Chemisty. 10. 2266-2269 (2000)
[Publications] 松島光一他: "Crystal Structure of an Ionic Charge-Transfer Complex of DAP-F_4TCNQ (DAP=1,6-Diaminopyrene, F_4TCNQ=2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane)"Bulletin of the Chemistry Society of Japan. 73. 2231-2235 (2000)
[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] 池上敬一他: "Structural Change in Langmuir and Langmuir-Blodgett Films of AlkylDCNQI Induced by Charge-Transfer Reaction at the Air-Water Interface"Journal of Chemical Physics. 112. 881-886 (2000)
[Publications] K.Uesugi、他: "Temperature Dependence of Band Gap Energies of GaAsN Alloys"Applied Physics Letters. 76. 1285-1287 (2000)
[Publications] Y.Abe、他: "Polymerization of Pyrrole under Microgravity Conditions"Space Forum. 6. 221-226 (2000)
[Publications] 長谷川達生他: "Mixed-Stack Organic Charge-Transfer Complexes with Intercolumnar Networks"Physical Review B. 62. 10059-10066 (2000)
[Publications] 芥川智行他: "Crystal Structure of Tetrathiafulvalene Multiannulated Macrocycles in Open-Shell Electronic State"Molecular Crystals and Liquid Crystals. 349. 379-382 (2000)
[Publications] 中村貴義他: "Conducting Langmuir-Blodgett Films of Bis[bis(methylthio)tetrathiafulvalenedithiolate]-gold Complex"Chemistry Letters. 134-135 (2001)

2000 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] 高松信博 他: "One-Dimensional Antiferromagnetic Chain in [Ni(dmit)_2]^- Salts of [K^+ or Rb^+ (4,13-diaza-18-crown-6)] Supramolecular Cation"Inorganic Chemistry. 39(5). 870-871 (2000)

[Publications] 芥川智行 他: "M^+ (12-crown-4) Supramolecular Cations (M^+=Na^+,K^+,Rb^+,and NH_4^+) within Ni (2-thioxo-1,3-dithiole-4,5-dithiolate)_2 Molecular Conductor"Inorganic Chemistry. 39(12). 2645-2651 (2000)

[Publications] 芥川智行 他: "Co^<2+> (15-crown-5) Magnetic Supramolecular Cation in [Ni(dmit)_2]^-π-Spin System"The Journal of Physical Chemistry B. 104(25). 5871-5873 (2000)

[Publications] 花咲徳亮 他: "Giant Negative Magnetoresistance in One- Dimensional π-d System : TPP[Fe(Pc)(CN)_2]_2(TPP=tetraphenylphosphonium,Pc=phthalocyanine)"Molecular Crystals and Liquid Crystals. 343. 41-46 (2000)

[Publications] 高松信博 他: "M^+(Crown Ether) Supramolecular Cations (M^+=K^+, Rb^+, NH_4^+) for Controlling Magnetic Properties of Monovalent [Ni(dmit)_2] Salts"Molecular Crystals and Liquid Crystals. 343. 163-168 (2000)

[Publications] 花咲徳亮 他: "Giant Negative Magnetoresistance in Quasi-One-Dimensional Conductor TPP[Fe(Pc)(CN)_2]_2 : Interplay between Local Moments and One-Dimensional Conduction Electrons"Physical Review B. 62(9). 5839-5842 (2000)

[Publications] 松村直子 他: "Multi-Dimensional π-π Stacking Interaction in Neutral Radical Crystals Obtained by Electrochemical Oxidation of [Co^<III>(2,3-Nc)(CN)_2]^- (2,3-Nc=2,3-naphthalocyanine)"Journal Materials Chemisty. 10. 2266-2269 (2000)

[Publications] 松島光一 他: "Crystal Structure of an Ionic Charge-Transfer Complex of DAP-F_4TCNQ (DAP=1,6-Diaminopyrene, F_4TCNQ=2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane)"Bulletin of the Chemistry Society of Japan. 73. 2231-2235 (2000)

[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] 池上敬一 他: "Structural Change in Langmuir and Langmuir-Blodgett Films of AlkylDCNQI Induced by Charge-Transfer Reaction at the Air-Water Interface"Journal of Chemical Physics. 112. 881-886 (2000)

[Publications] K.Uesugi、 他: "Temperature Dependence of Band Gap Energies of GaAsN Alloys"Applied Physics Letters. 76. 1285-1287 (2000)

[Publications] Y.Abe、 他: "Polymerization of Pyrrole under Microgravity Conditions"Space Forum. 6. 221-226 (2000)

[Publications] 長谷川達生 他: "Mixed-Stack Organic Charge-Transfer Complexes with Intercolumnar Networks"Physical Review B. 62. 10059-10066 (2000)

[Publications] 芥川智行 他: "Crystal Structure of Tetrathiafulvalene Multiannulated Macrocycles in Open-Shell Electronic State"Molecular Crystals and Liquid Crystals. 349. 379-382 (2000)

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

稲辺保北海道大学, 大学院・理学研究科, 教授 (20168412)

[Publications] 高松信博他: "One-Dimensional Antiferromagnetic Chain in [Ni(dmit)_2]^- Salts of [K^+ or Rb^+ (4,13-diaza-18-crown-6)] Supramolecular Cation"Inorganic Chemistry. 39(5). 870-871 (2000)

[Publications] 芥川智行他: "M^+ (12-crown-4) Supramolecular Cations (M^+=Na^+,K^+,Rb^+,and NH_4^+) within Ni (2-thioxo-1,3-dithiole-4,5-dithiolate)_2 Molecular Conductor"Inorganic Chemistry. 39(12). 2645-2651 (2000)

[Publications] 芥川智行他: "Co^<2+> (15-crown-5) Magnetic Supramolecular Cation in [Ni(dmit)_2]^-π-Spin System"The Journal of Physical Chemistry B. 104(25). 5871-5873 (2000)

[Publications] 花咲徳亮他: "Giant Negative Magnetoresistance in One- Dimensional π-d System : TPP[Fe(Pc)(CN)_2]_2(TPP=tetraphenylphosphonium,Pc=phthalocyanine)"Molecular Crystals and Liquid Crystals. 343. 41-46 (2000)

[Publications] 高松信博他: "M^+(Crown Ether) Supramolecular Cations (M^+=K^+, Rb^+, NH_4^+) for Controlling Magnetic Properties of Monovalent [Ni(dmit)_2] Salts"Molecular Crystals and Liquid Crystals. 343. 163-168 (2000)

[Publications] 花咲徳亮他: "Giant Negative Magnetoresistance in Quasi-One-Dimensional Conductor TPP[Fe(Pc)(CN)_2]_2 : Interplay between Local Moments and One-Dimensional Conduction Electrons"Physical Review B. 62(9). 5839-5842 (2000)

[Publications] 松村直子他: "Multi-Dimensional π-π Stacking Interaction in Neutral Radical Crystals Obtained by Electrochemical Oxidation of [Co^<III>(2,3-Nc)(CN)_2]^- (2,3-Nc=2,3-naphthalocyanine)"Journal Materials Chemisty. 10. 2266-2269 (2000)

[Publications] 松島光一他: "Crystal Structure of an Ionic Charge-Transfer Complex of DAP-F_4TCNQ (DAP=1,6-Diaminopyrene, F_4TCNQ=2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane)"Bulletin of the Chemistry Society of Japan. 73. 2231-2235 (2000)

[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] 池上敬一他: "Structural Change in Langmuir and Langmuir-Blodgett Films of AlkylDCNQI Induced by Charge-Transfer Reaction at the Air-Water Interface"Journal of Chemical Physics. 112. 881-886 (2000)

[Publications] K.Uesugi、他: "Temperature Dependence of Band Gap Energies of GaAsN Alloys"Applied Physics Letters. 76. 1285-1287 (2000)

[Publications] Y.Abe、他: "Polymerization of Pyrrole under Microgravity Conditions"Space Forum. 6. 221-226 (2000)

[Publications] 長谷川達生他: "Mixed-Stack Organic Charge-Transfer Complexes with Intercolumnar Networks"Physical Review B. 62. 10059-10066 (2000)

[Publications] 芥川智行他: "Crystal Structure of Tetrathiafulvalene Multiannulated Macrocycles in Open-Shell Electronic State"Molecular Crystals and Liquid Crystals. 349. 379-382 (2000)

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