2003 Fiscal Year Annual Research Report

多様な積層構造をもつフタロシアニンπ-d系導電体の構築

Research Project

Project/Area Number	15073101
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)	石田尚行電気通信大学, 電気通信部, 助教授 (00232306) 野上隆電気通信大学, 電気通信部, 教授 (80029280)
Keywords	分子性固体 / 有機導体 / 磁性導電体 / 結晶設計 / π-d相互作用
Research Abstract	フタロシアニン(Pc)系では母体のCo錯体をPXX(6,12-dioxaanthanthrene)とともに電解酸化したとき、[PXX]_2[Co(Pc)(CN)_2]の組成の針状結晶が得られることを見出した。この構造はPc unitが二次元的なπ積層構造で配列し、部分酸化状態であることが分かった。室温伝導度は1000S cm^<-1>で、金属的な温度変化を示し低温でも高伝導性である。この高伝導性は二次元的な積層構造に由来しているが、反射スペクトルにより二次元面内での相互作用は異方的であることが分かった。一方、電解で一緒に得られる[PXX]_2[Co(Pc)(CN)_2]・CH_3CNの組成の板状晶でもPc部が部分酸化状態であることがESR測定から新たに判明し、結晶中ではより等方的な二次元構造となっていることが示された。現在、この結晶の物性を調べているが、同時に二次元π-d系を構築するためFe(Pc)(CN)_2 unitを用いた結晶作成も進めている。また、一次元Fe系で見出された巨大な負の磁気抵抗の起源を探る目的で、分子レベルでの磁気的な性質を調べ、大きな磁気異方性の起源となる軌道を明らかにした。 π-d系磁性伝導体の開発として、野上・石田グループは、ジオキサジセレナフルバレン骨格をもつ新しいドナーやテトラオキサ及びジオキサジチアフルバレンを用いることを計画し、これらのドナー性、ラジカルカチオンの安定性、結晶構造中における分子間相互作用などを系統的に調べた。平行して、銅イオンとランタノイドイオンをもつ基底スピンが非常に大きい多核錯イオンを開発した。これらを上記有機ドナー分子と組み合わせることで、π-d-fヘテロ電子系磁性導体となると期待される。また、超分子的磁性材料を合成し、キラル磁性体の構造と性質を明らかにし、また、多孔質磁性体を開発し、ホストゲスト科学による磁性チューニングを示した。

Research Products

(34 results)

All Other

All Publications (34 results)

[Publications] K.Takeda: "Magnetic Anisotropy, Tunneling Effects, High-Frequency EPR and Molecular Structure of Fast Relaxation Species of Mn_<12>"Physical Review B. 65. 4424-4424 (2002)
[Publications] T.Inabe: "Controlled π-π Stacking Structure in Phthalocyanine-based Conducors"Liquid Crystals. 376. 225-232 (2002)
[Publications] N.Kobayasi: "Novel Ni-Dithiolene Complexes toward Lattice Architecture"Molecular Crystals and Liquid Crystals. 376. 233-238 (2002)
[Publications] T.Akutagawa: "Supramolecuar Cation Assemblies of Hydrogen-Bonded(NH_4^+/NH_2NH_3^+)(Crown Ether) in [Ni(dmit)_2]-Based Molecular Conductors and Magnets"J.Am.Chem.Soc.. 124. 8903-8911 (2002)
[Publications] T.Naito: "Synthesis of New Dithiolene-Derivative Metal Complexes"Molecular Crystals and Liquid Crystals. 380. 245-250 (2002)
[Publications] M.Matsuda: "One-Dimensional π-d System with Axially Substituted Iron(III) Phthalocyanine"Molecular Crystals and Liquid Crystals. 380. 277-282 (2002)
[Publications] T.Akutagawa: "Coupled Protonic and Electronic Conductin in the Molecular Conductor [2-(2-1H-Benzimidazolyl)- 1H-benzimidazolium]-TCNQ"Chemistry A European Journal. 8. 4402-4411 (2002)
[Publications] T.Hirose: "Charge Carrier Doping in the Ni(dmit)_2 Simple Salts by Hydrogen-Bonding Pyridinium Cations (dmit=1,3-dithiol-2-thione-4,5-dithiolate)"Jurnal of Solid State Chemistory. 168. 535-546 (2002)
[Publications] H.Tajima: "Magnetoresistance Study on TPP[M(Pc)(CN)_2]_2(M=Fe,Co,Fe_<0.30>Co_<0.07>)salts"Jurnal of Solid State Chemistory. 168. 509-513 (2002)
[Publications] N.Hanasaki: "One-dimensional π-d electoron system in TPP[Fe(Pc)(CN)_2]_2,[PXX][Fe(Pc)(CN)_2], and (PTMA)_X[Fe(Pc)(CN)_2]_Y(CH_3CN) : electpron spin resonance and negative magnetoresistance"Synthetic Metals. 133-134. 519-521 (2003)
[Publications] T.Inabe: "Phthalocyanine-based multi-dimensional conductors"Synthetic Metals. 133-134. 515-518 (2003)
[Publications] T.Naito: "ET_3(MnCl_3),(EtOH)_2 : a new organic conductor with a perovskite structure"Synthetic Metals. 133-134. 445-447 (2003)
[Publications] M.Matsuda: "Magnetic and optical properties of one-dimensional π-d system with axially substituted iron(III) phthalocyanine"Synthetic Metals. 133-134. 547-548 (2003)
[Publications] M.Matsuda: "Magnetic Properties of d-π Conducting System, TPP[Fe^<III>_xCo^<III>_<1-x>(Pc)(CN)_2]_2"Synthetic Metals. 135-136. 635-636 (2003)
[Publications] N.Hanasaki: "Torque study of TPP[Fe(Pc)(CN)_2]_2 (TPP=tetraphenyl phosphonium and Pc=phthalocyanine)"Synthetic Metals. 137. 1227-1228 (2003)
[Publications] T.Naito: "Physical Properties of (ET)_3(MnCl_4)(TCE) and the Related Salts"Synthetic Metals. 135-136. 613-614 (2003)
[Publications] N.Kobayashi: "Hydrogen-Bond Networks of Mellitate Anions ([C_6(COO)_6H_<6-n>]^<n->) in Salts with Pyridine Derivatives"Bulletin of the Chemistry Society of Japan. 76. 1351-1362 (2003)
[Publications] M.Matsuda: "Structure and Physical Properties of Low-Dimensional Molecular Conductors, [PXX][Fe^<III>(Pc)(CN)_2] and [PXX][Co^<III>(Pc)(CN)_2](PXX=peri-xanthenoxanthene, Pc=phthalocyaninato)"Bulletin of the Chemistry Society of Japan. 76. 1935-1940 (2003)
[Publications] N.Hanasaki: "Contribution of Degenerate Molecular Orbitals to Molecular Orbital Angular Momentum in Molecular Magnet Fe(Pc)(CN)_2"Journal of the Physical Society of Japan. 72. 3226-3230 (2003)
[Publications] K.Doi: "Nitronyl Nitroxide Substituted Aniline o-APNN with a Three-Dimensional Hydrogen Bond Network Showing Ferromagnetic Interaction"Chem.Lett.. 32. 544-545 (2003)
[Publications] C.Aoki: "Metamagnetic Behavior of [Ni(4ImNNH)_2(NO_3)_2] Having a Ground High-Spin State (4ImNNH=4-Imidazolyl Nitronyl Nitroxide)"Inorg.Chem.Commun.. 6. 1122-1125 (2003)
[Publications] Y.Kobayashi: "Rectangular Tetragadolinium Complex ion with a Ground S=27/2 State Containing Bis(dimethylglyoximato)copper(II) as a Ferrimagnetic Exchange Coupler"Chem.Phys.Lett.. 378. 337-342 (2003)
[Publications] T.Ise: "Ferro- and Ferrimagnetic Chains of hin-Bridged Copper(II) and Manganese(II) and hnn-Bridged Manganese(II) Complexes (hin=4,4,5,5-Tetramethylimidazolin-1-oxyl ; hnn=4,4,5,5-Tetramethylimidazolin-1-oxyl 3-Oxide)"Inorg.Chem.. 42. 6106-6113 (2003)
[Publications] T.Ishida: "A Self-Assembled Helix from 4,6-Dimethylpyrimidine and Copper(II) Bromide"Chem.Lett.. 32. 1018-1019 (2003)
[Publications] C.Aoki: "A Molecular Metamagnet [Ni(4ImNNH)_2(NO_3)_2] (4ImNNH=4-Imidazolyl Nitronyl Nitroxide) and the Related Compounds Showing Supramolecular H-Bonding Interaction"Inorg.Chem.. 42. 7616-7625 (2003)
[Publications] T.Asano: "Effect of Staggered Field in S=1/2 Antiferromagnetic Chain : Copper Pyrimidine"Physica B : Cond.Matter. 329. 1006-1007 (2003)
[Publications] M.Seino: "Magnetic Properties of 9,9-Disubstituted 9,10-Dihydroacridine-10-yloxyls"Synth.Met.. 133-134. 581-583 (2003)
[Publications] T.Matsuyama: "Hybrid Magnetic Solids of Radical-Substituted Heteroaromatic Compounds with Metal Halides"Synth.Met.. 133-134. 611-613 (2003)
[Publications] G.Maruta: "Low Temperature Deuterium NMR Studies on Magnetism of TEMPO Derivatives"Synth.Met.. 133-134. 577-579 (2003)
[Publications] T.Ise: "Hydroiminonitroxide Complexes with Metal Hexafluoroacetylacetonates"Synth.Met.. 137. 1281-1282 (2003)
[Publications] T.Ishida: "Host-Guest Chemistry of Radical-Copper Wheels. A Supramolecular Control of Magnetic Exchange Coupling"Polyhedron. 22. 2133-2138 (2003)
[Publications] T.Ichimura: "meta-Phenylene-Bridged Bis(imino Nitroxide) Biradicals as Potential High-Spin Ligands"Polyhedron. 22. 2557-2564 (2003)
[Publications] S.Yamada: "Supramolecular Triangular and Linear Arrays of Metal-Radical Solids Using Imino-Nitroxide-Substituted Pyrazolate Bridges"Dalton Trans. 6. 898-903 (2004)
[Publications] T.Asari: "Novel Phthalocyanine Conductor Containing Two-dimensional Pc Stacks, [PXX]_2[Co(Pc)(CN)_2] (PXX=peri-Xanthenoxanthene, Co(Pc)(CN)_2=Dicyano(phthalocyaninato)cobalt(III))"Chemistry Letters. 33. 128-129 (2004)

2003 Fiscal Year Annual Research Report

多様な積層構造をもつフタロシアニンπ-d系導電体の構築

Principal Investigator

稲辺 保 北海道大学, 大学院・理学研究科, 教授 (20168412)

Research Products

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

[Publications] T.Inabe: "Controlled π-π Stacking Structure in Phthalocyanine-based Conducors"Liquid Crystals. 376. 225-232 (2002)

[Publications] N.Kobayasi: "Novel Ni-Dithiolene Complexes toward Lattice Architecture"Molecular Crystals and Liquid Crystals. 376. 233-238 (2002)

[Publications] T.Akutagawa: "Supramolecuar Cation Assemblies of Hydrogen-Bonded(NH_4^+/NH_2NH_3^+)(Crown Ether) in [Ni(dmit)_2]-Based Molecular Conductors and Magnets"J.Am.Chem.Soc.. 124. 8903-8911 (2002)

[Publications] T.Naito: "Synthesis of New Dithiolene-Derivative Metal Complexes"Molecular Crystals and Liquid Crystals. 380. 245-250 (2002)

[Publications] M.Matsuda: "One-Dimensional π-d System with Axially Substituted Iron(III) Phthalocyanine"Molecular Crystals and Liquid Crystals. 380. 277-282 (2002)

[Publications] T.Akutagawa: "Coupled Protonic and Electronic Conductin in the Molecular Conductor [2-(2-1H-Benzimidazolyl)- 1H-benzimidazolium]-TCNQ"Chemistry A European Journal. 8. 4402-4411 (2002)

[Publications] T.Hirose: "Charge Carrier Doping in the Ni(dmit)_2 Simple Salts by Hydrogen-Bonding Pyridinium Cations (dmit=1,3-dithiol-2-thione-4,5-dithiolate)"Jurnal of Solid State Chemistory. 168. 535-546 (2002)

[Publications] H.Tajima: "Magnetoresistance Study on TPP[M(Pc)(CN)_2]_2(M=Fe,Co,Fe_<0.30>Co_<0.07>)salts"Jurnal of Solid State Chemistory. 168. 509-513 (2002)

[Publications] N.Hanasaki: "One-dimensional π-d electoron system in TPP[Fe(Pc)(CN)_2]_2,[PXX][Fe(Pc)(CN)_2], and (PTMA)_X[Fe(Pc)(CN)_2]_Y(CH_3CN) : electpron spin resonance and negative magnetoresistance"Synthetic Metals. 133-134. 519-521 (2003)

[Publications] T.Inabe: "Phthalocyanine-based multi-dimensional conductors"Synthetic Metals. 133-134. 515-518 (2003)

[Publications] T.Naito: "ET_3(MnCl_3),(EtOH)_2 : a new organic conductor with a perovskite structure"Synthetic Metals. 133-134. 445-447 (2003)

[Publications] M.Matsuda: "Magnetic and optical properties of one-dimensional π-d system with axially substituted iron(III) phthalocyanine"Synthetic Metals. 133-134. 547-548 (2003)

[Publications] M.Matsuda: "Magnetic Properties of d-π Conducting System, TPP[Fe^<III>_xCo^<III>_<1-x>(Pc)(CN)_2]_2"Synthetic Metals. 135-136. 635-636 (2003)

[Publications] N.Hanasaki: "Torque study of TPP[Fe(Pc)(CN)_2]_2 (TPP=tetraphenyl phosphonium and Pc=phthalocyanine)"Synthetic Metals. 137. 1227-1228 (2003)

[Publications] T.Naito: "Physical Properties of (ET)_3(MnCl_4)(TCE) and the Related Salts"Synthetic Metals. 135-136. 613-614 (2003)

[Publications] N.Kobayashi: "Hydrogen-Bond Networks of Mellitate Anions ([C_6(COO)_6H_<6-n>]^<n->) in Salts with Pyridine Derivatives"Bulletin of the Chemistry Society of Japan. 76. 1351-1362 (2003)

[Publications] M.Matsuda: "Structure and Physical Properties of Low-Dimensional Molecular Conductors, [PXX][Fe^<III>(Pc)(CN)_2] and [PXX][Co^<III>(Pc)(CN)_2](PXX=peri-xanthenoxanthene, Pc=phthalocyaninato)"Bulletin of the Chemistry Society of Japan. 76. 1935-1940 (2003)

[Publications] N.Hanasaki: "Contribution of Degenerate Molecular Orbitals to Molecular Orbital Angular Momentum in Molecular Magnet Fe(Pc)(CN)_2"Journal of the Physical Society of Japan. 72. 3226-3230 (2003)

[Publications] K.Doi: "Nitronyl Nitroxide Substituted Aniline o-APNN with a Three-Dimensional Hydrogen Bond Network Showing Ferromagnetic Interaction"Chem.Lett.. 32. 544-545 (2003)

[Publications] C.Aoki: "Metamagnetic Behavior of [Ni(4ImNNH)_2(NO_3)_2] Having a Ground High-Spin State (4ImNNH=4-Imidazolyl Nitronyl Nitroxide)"Inorg.Chem.Commun.. 6. 1122-1125 (2003)

[Publications] Y.Kobayashi: "Rectangular Tetragadolinium Complex ion with a Ground S=27/2 State Containing Bis(dimethylglyoximato)copper(II) as a Ferrimagnetic Exchange Coupler"Chem.Phys.Lett.. 378. 337-342 (2003)

[Publications] T.Ise: "Ferro- and Ferrimagnetic Chains of hin-Bridged Copper(II) and Manganese(II) and hnn-Bridged Manganese(II) Complexes (hin=4,4,5,5-Tetramethylimidazolin-1-oxyl ; hnn=4,4,5,5-Tetramethylimidazolin-1-oxyl 3-Oxide)"Inorg.Chem.. 42. 6106-6113 (2003)

[Publications] T.Ishida: "A Self-Assembled Helix from 4,6-Dimethylpyrimidine and Copper(II) Bromide"Chem.Lett.. 32. 1018-1019 (2003)

[Publications] C.Aoki: "A Molecular Metamagnet [Ni(4ImNNH)_2(NO_3)_2] (4ImNNH=4-Imidazolyl Nitronyl Nitroxide) and the Related Compounds Showing Supramolecular H-Bonding Interaction"Inorg.Chem.. 42. 7616-7625 (2003)

[Publications] T.Asano: "Effect of Staggered Field in S=1/2 Antiferromagnetic Chain : Copper Pyrimidine"Physica B : Cond.Matter. 329. 1006-1007 (2003)

[Publications] M.Seino: "Magnetic Properties of 9,9-Disubstituted 9,10-Dihydroacridine-10-yloxyls"Synth.Met.. 133-134. 581-583 (2003)

[Publications] T.Matsuyama: "Hybrid Magnetic Solids of Radical-Substituted Heteroaromatic Compounds with Metal Halides"Synth.Met.. 133-134. 611-613 (2003)

[Publications] G.Maruta: "Low Temperature Deuterium NMR Studies on Magnetism of TEMPO Derivatives"Synth.Met.. 133-134. 577-579 (2003)

[Publications] T.Ise: "Hydroiminonitroxide Complexes with Metal Hexafluoroacetylacetonates"Synth.Met.. 137. 1281-1282 (2003)

[Publications] T.Ishida: "Host-Guest Chemistry of Radical-Copper Wheels. A Supramolecular Control of Magnetic Exchange Coupling"Polyhedron. 22. 2133-2138 (2003)

[Publications] T.Ichimura: "meta-Phenylene-Bridged Bis(imino Nitroxide) Biradicals as Potential High-Spin Ligands"Polyhedron. 22. 2557-2564 (2003)

[Publications] S.Yamada: "Supramolecular Triangular and Linear Arrays of Metal-Radical Solids Using Imino-Nitroxide-Substituted Pyrazolate Bridges"Dalton Trans. 6. 898-903 (2004)

[Publications] T.Asari: "Novel Phthalocyanine Conductor Containing Two-dimensional Pc Stacks, [PXX]_2[Co(Pc)(CN)_2] (PXX=peri-Xanthenoxanthene, Co(Pc)(CN)_2=Dicyano(phthalocyaninato)cobalt(III))"Chemistry Letters. 33. 128-129 (2004)

稲辺保北海道大学, 大学院・理学研究科, 教授 (20168412)