1993 Fiscal Year Annual Research Report

新しい分子磁性系の設計と構築

Research Project

Project/Area Number	04242104
Research Institution	Kyoto University
Principal Investigator	杉本豊成京都大学, 工学部, 助教授 (30093256)
Co-Investigator(Kenkyū-buntansha)	大川尚士九州大学, 理学部, 教授 (00037219) 菅原正東京大学, 教養学部, 教授 (50124219) 西出宏之早稲田大学, 理工学部, 教授 (90120930) 蒲池幹治大阪大学, 理学部, 教授 (40028163)
Keywords	電荷移動錯体 / ラジカル結晶 / アニオンラジカル / ポリマー / 遷移金属錯体 / 三架橋D_3対称性 / 強磁性体 / フェリ磁性体
Research Abstract	今年度の研究実施により以下に示す研究成果を得た。(1)空気中で安定な3つの電荷移動(CT)錯体、ピリジニウム置換イミダゾリン-1-オキシル/テトラフルオロ置換TCNQ(TCNQF_4)およびヘキサシアノブタジエンのアニオンラジカルにおいて初めて強磁性的相互作用が見いだされ、CT錯体による純有機強磁性体の可能性が拓かれた(杉本)。(2)新たに設計・構築したニトロキシドについて、強磁性的相互作用する有機ラジカル結晶が見いだされた(蒲池)。また、TCNQF_4ラジカルアニオンのリチウム塩が12K以下で弱強磁性を示すことを明らかにした(杉本)。スピン多重度が2および3と相異なる2つの安定ニトロキシドラジカルの混晶が交互積層構造を形成し、結晶中で両者のスピン間に反強磁性的相互作用が働いて、秩序形成の距離は短いが、純有機系結晶で初めて部分的なフェリ磁性が実現された(菅原)。(3)高分子のパイ共役主鎖にポリフェニレンビニレンを用いることにより、側鎖上に置かれたラジカル間に高分子では初めて強磁性的なスピン相互作用が見いだされた(西出)。(4)三架橋性D_3対称の常磁性金属錯体、トリスオキサラトクロム酸(III)イオンを素子として、マンガン、鉄、コバルト、ニッケル、銅の2価イオンを対イオンとする強磁性錯体を合成することに成功した。最も高い磁気転移温度(キューリー温度)として14Kが得られた(大川)。さらに、配位子をオキサラトからジチオオキサラトに替えたときに得られる三架橋性D_3対称ニッケル/クロム金属錯体もまた強磁性体になり、そのキューリー温度は23Kで、対応するオキサラト類縁体よりも8K近くも向上した(大川)。

Research Products

(14 results)

All Other

All Publications (14 results)

[Publications] 杉本豊成: "Ferromagnetic Interaction in Organic Radical Salts" Molecular Crystals and Liquid Crystals. 232. 117-134 (1993)
[Publications] 杉本豊成: "Intramolecular Spin-spin Exchange in Cation Radicals of Tetrathiafulvalene Derivatives Substituted with Imino Pyrolidine-1-oxyl" Chemistry Letters. 1361-1364 (1993)
[Publications] 杉本豊成: "Spin-spin Coupling between the Two Unpaired Electrons in Bis(tetrathiafulvalenyl)ketone Dications" Advanced Materials. 5. 741-743 (1993)
[Publications] 杉本豊成: "Different Magnetic Properties of Charge-transfer Complexes and Cation Radical Salts of Tetrathiafulvalene Derivatives" Chemistry Letters. 1817-1820 (1993)
[Publications] 蒲池幹治: "Ferromagnetic and Antiferromagnetic Behaviors of 4-Methacryloyl- and 4-Acryloxyl-2,2,6,6-tetramethylpiperidine-1-oxyls" Molecular Crystals and Liquid Crystals. 232. 53-60 (1993)
[Publications] 西出宏之: "Polyacetylene Derivatives with Chain-sided Phenoxy and Galvinoxyl Radicals" Molecular Crystals and Liquid Crystals. 233. 89-96 (1993)
[Publications] 西出宏之: "Poly(phenylvinylene) and Poly(phemylenevinylene) with Nitroxide Radicals" Molecular Crystals and Liquid Crystals. 232. 143-150 (1993)
[Publications] 西出宏之: "Poly(4-(N-tert-butyl-N-hydroxyamino)phenyl)acetylene and the Magnetic Property of Its Radical Derivatives" Macromolecules. 26. 4567-4571 (1993)
[Publications] 菅原正: "Stable Mono-,Di-,and Triradicals as Constituent Molecules for Organic Ferrimagnets" Molecular Crystals and Liquid Crystals. 232. 103-108 (1993)
[Publications] 菅原正: "Preparation of Tetrathiafulvaleno-nitronylnitroxide and Magnetic Properties of Its DDQ Complex" Molecular Crystals and Liquid Crystals. 232. 151-154 (1993)
[Publications] 大川尚士: "Synthesis and Ferromagnetic Spin-coupling of an Imidazolate-bridged 3d-4d Cu(II)-Ru(III) Binuclear Complex" Chemistry Letters. 1433-1436 (1993)
[Publications] 大川尚士: "Ferrimagnetic Mixed-metal Assemblies(NBu_4(MFe(ox)_3)_x" Molecular Crystals and Liquid Crystals. 233. 257-262 (1993)
[Publications] 大川尚士: "Moessbauer Spectroscopy Study of Magnetic Ordering in Oxalate-bridged Cr(III)-Fe(II) and Fe(III)-Fe(II) Systems" Molecular Crystals and Liquid Crystals. 233. 263-268 (1993)
[Publications] 大川尚士: "Ferromagnetic Spin-coupling of Several Homo- and Mixed-metal Complexes" Molecular Crystals and Liquid Crystals. 233. 299-308 (1993)

1993 Fiscal Year Annual Research Report

新しい分子磁性系の設計と構築

Principal Investigator

杉本 豊成 京都大学, 工学部, 助教授 (30093256)

Research Products

[Publications] 杉本豊成: "Ferromagnetic Interaction in Organic Radical Salts" Molecular Crystals and Liquid Crystals. 232. 117-134 (1993)

[Publications] 杉本豊成: "Intramolecular Spin-spin Exchange in Cation Radicals of Tetrathiafulvalene Derivatives Substituted with Imino Pyrolidine-1-oxyl" Chemistry Letters. 1361-1364 (1993)

[Publications] 杉本豊成: "Spin-spin Coupling between the Two Unpaired Electrons in Bis(tetrathiafulvalenyl)ketone Dications" Advanced Materials. 5. 741-743 (1993)

[Publications] 杉本豊成: "Different Magnetic Properties of Charge-transfer Complexes and Cation Radical Salts of Tetrathiafulvalene Derivatives" Chemistry Letters. 1817-1820 (1993)

[Publications] 蒲池幹治: "Ferromagnetic and Antiferromagnetic Behaviors of 4-Methacryloyl- and 4-Acryloxyl-2,2,6,6-tetramethylpiperidine-1-oxyls" Molecular Crystals and Liquid Crystals. 232. 53-60 (1993)

[Publications] 西出宏之: "Polyacetylene Derivatives with Chain-sided Phenoxy and Galvinoxyl Radicals" Molecular Crystals and Liquid Crystals. 233. 89-96 (1993)

[Publications] 西出宏之: "Poly(phenylvinylene) and Poly(phemylenevinylene) with Nitroxide Radicals" Molecular Crystals and Liquid Crystals. 232. 143-150 (1993)

[Publications] 西出宏之: "Poly(4-(N-tert-butyl-N-hydroxyamino)phenyl)acetylene and the Magnetic Property of Its Radical Derivatives" Macromolecules. 26. 4567-4571 (1993)

[Publications] 菅原正: "Stable Mono-,Di-,and Triradicals as Constituent Molecules for Organic Ferrimagnets" Molecular Crystals and Liquid Crystals. 232. 103-108 (1993)

[Publications] 菅原正: "Preparation of Tetrathiafulvaleno-nitronylnitroxide and Magnetic Properties of Its DDQ Complex" Molecular Crystals and Liquid Crystals. 232. 151-154 (1993)

[Publications] 大川尚士: "Synthesis and Ferromagnetic Spin-coupling of an Imidazolate-bridged 3d-4d Cu(II)-Ru(III) Binuclear Complex" Chemistry Letters. 1433-1436 (1993)

[Publications] 大川尚士: "Ferrimagnetic Mixed-metal Assemblies(NBu_4(MFe(ox)_3)_x" Molecular Crystals and Liquid Crystals. 233. 257-262 (1993)

[Publications] 大川尚士: "Moessbauer Spectroscopy Study of Magnetic Ordering in Oxalate-bridged Cr(III)-Fe(II) and Fe(III)-Fe(II) Systems" Molecular Crystals and Liquid Crystals. 233. 263-268 (1993)

[Publications] 大川尚士: "Ferromagnetic Spin-coupling of Several Homo- and Mixed-metal Complexes" Molecular Crystals and Liquid Crystals. 233. 299-308 (1993)

杉本豊成京都大学, 工学部, 助教授 (30093256)