2001 Fiscal Year Annual Research Report

分子磁性の超分子的制御

Research Project

Project/Area Number	13640575
Research Institution	The University of Electro-Communications
Principal Investigator	石田尚行電気通信大学, 電気通信学部, 助教授 (00232306)
Co-Investigator(Kenkyū-buntansha)	野上隆電気通信大学, 電気通信学部, 教授 (80029280)
Keywords	ピリミジン / 有機ラジカル / 有機強磁性体 / 磁気的相転移 / 分子性磁性体 / ホストゲスト化学 / 結晶工学
Research Abstract	有機・分子性強磁性体を題材にして、超分子手法を用いて強磁性的-反強磁性的相互作用をスイツチしたり、分子の基底スピン多重度を変化させたり、スピンを発生あるいは消滅させるといったような、動的に磁性を制御することを目指した。超分子手法とは、ホスト・ゲスト分子間の相互作用、小さな分子の吸着脱離、あるいはケージ内反応などを指す。ピリミジン(PM)およびN(CN)_2^-の架橋配位子を用いた錯体では、ゲスト分子が結晶の格子の間に取り込まれることがわかった。Fe[N(CN)_2]_2PM・(guest)の結晶構造は、ゲスト分子がエタノール、プロパノール、ブタノールおよびピリミジンのときに同形結晶を与え、磁気的相転移温度はそれぞれ3. 3, 4. 4, 3. 6, 5. 6Kであった。液体ヘリウム温度領域における2Kの差はかなり大きいものである。これらは弱強磁性体であり、その傾角もゲスト分子に大きく依存した。なお、この系を発展させて別のアニオンを用いた場合に、転移温度が50K級のものも見いだした。 [4PMNN・C_ux_2]_6(X=Cl, B_r)は、12スピン系大員環状の分子構造を有し、結晶中ではカラムを形成する(4PMNNは4位にニトロニルニトロキシドラジカル基を有するピリミジン)。チューブ状空間にゲスト分子として有機分子やハロゲン化アルカリ金属塩を取り込ませたところ、強磁性的相互作用が増大した。ゲストとして水を用いたものは、ポンピングによる脱水の前後で、磁性を大きく変化させることができた。

Research Products

(18 results)

All Other

All Publications (18 results)

[Publications] J.Omata, 他4名: "Radical-Copper Wheels : Structure and Magnetism of Hexanuclear Hybrid Arrays"Inorganic Chemistry. 40. 3954-3958 (2001)
[Publications] T.Ishida, 他5名: "Ferromagnetic Exchange Coupling of Vanadium(IV)dπ Spins across Pyrimidine Rings : Dinuclear Complexes of Oxovanadium(IV)..."Inorganic Chemistry. 40. 7059-7064 (2001)
[Publications] M.Yasui, 他5名: "Dipyrimidine-Cu(II)Dinitrate Complexes Showing Magnetic Interactions"Acta Crystallographica Section B. 57. 288-295 (2001)
[Publications] M.Yasui, 他4名: "Bis(hfac)-Copper(ll)Complexes Bridged by Pyrimidines Showing Magnetic Interactions"Acta Crystallographica Section B. 57. 772-779 (2001)
[Publications] M.Mito 他5名: "Pressure Effects of Genuine Organic Crystalline Ferromagnet Possessing Intermolecular Contacts between Nitroxide Oxygen and ..."Chemical Physics Letters. 333. 69-75 (2001)
[Publications] T.Suzuki 他8名: "Single-Component Organic Semiconductors Based on Novel Radicals that Exhibit Electrochemical Amphotericity : Preparation, Crystal..."Journal of Organic Chemistry. 66. 216-224 (2001)
[Publications] T.Katayama 他2名: "Novel Organic-Inorganic Molecular Assembiy : s Copper(I)and Copper(II)Mixed-Valent Cluster with Bromide Bridges and ..."Inorganic Chimica Acta. 329. 31-35 (2002)
[Publications] T.Nogami 他3名: "Synthesis and Properties of New Oxygen-Corntaning Fulvalene Derivatives : Dibenzo-and Dinaphthotetraoxafulvalenes and ..."Synthetic Metals. 120. 755-756 (2001)
[Publications] J.Omata, 他4名: "Radical-Copper Hexanuclear Arrays Showing Ferrpmagnetic Interactions"Polyhedron. 20. 1557-1591 (2001)
[Publications] T.Miyake, 他4名: "Ferromagnetic S=1 Chain Formed by a Square Ni_2S_2Motif in Ni(qt)2(qt=Quinoline-8-thiolate). Magnetic Properties of Related..."Polyhedron. 20. 1551-1555 (2001)
[Publications] T.Ishida, 他4名: "Zero-Field Muon Spin Rotation Study on TEMPO-Based Magnets, Ar-CH=TEMPO"Polyhedron. 20. 1545-1549 (2001)
[Publications] S.Ohira, 他6名: "Anomalous Magnetism in ~Organic Radical Ferromagnets, 4-Arylmethyleneamino-2, 2, 6, 6-tetramethylpiperidin-yloxyl just above..."Polyhedron. 20. 772-779 (2001)
[Publications] J.Omata, 他4名: "Radical-Copper Macrocycles and Related Compounds"Molecular Crystals and Liquid Crystals. (印刷中). (2002)
[Publications] T.Kusaka, 他4名: "Magnetic Phase Transition of Fe^<II>, Co^<II>, and Ni^<II> Complexes Bridged by Pyrimidine and Dicyanamide"Molecular Crystals and Liquid Crystals. (印刷中). (2002)
[Publications] M.Seino, 他3名: "Magnetic Properties of 9, 9-Disubstituted 9, 10-dihydroacridine-10-yloxyls"Synthetic Metals. (印刷中). (2002)
[Publications] T.Matsuyama, 他3名: "Hybrid Magnetic Solids of Radical-Substituted Heteroaromatic Compounds with Metal Halides"Synthetic Metals. (印刷中). (2002)
[Publications] T.Kusaka, 他2名: "Solvated Magnets of F_e[N(CN)2](pyrimidine) : Transition Phenomena Tuned by Guests"Molecular Crystals and Liquid Crystals. (印刷中). (2002)
[Publications] T.Ise, 他2名: "First Isolation and Characterization of an HIN Complex, C_dCl_2(HIN)4(HIN=4, 4, 5, 5-Tetramethylimidazolin-1-oxyl)"Molecular Crystals and Liquid Crystals. (印刷中). (2002)

2001 Fiscal Year Annual Research Report

分子磁性の超分子的制御

Principal Investigator

石田 尚行 電気通信大学, 電気通信学部, 助教授 (00232306)

Research Products

[Publications] J.Omata, 他4名: "Radical-Copper Wheels : Structure and Magnetism of Hexanuclear Hybrid Arrays"Inorganic Chemistry. 40. 3954-3958 (2001)

[Publications] T.Ishida, 他5名: "Ferromagnetic Exchange Coupling of Vanadium(IV)dπ Spins across Pyrimidine Rings : Dinuclear Complexes of Oxovanadium(IV)..."Inorganic Chemistry. 40. 7059-7064 (2001)

[Publications] M.Yasui, 他5名: "Dipyrimidine-Cu(II)Dinitrate Complexes Showing Magnetic Interactions"Acta Crystallographica Section B. 57. 288-295 (2001)

[Publications] M.Yasui, 他4名: "Bis(hfac)-Copper(ll)Complexes Bridged by Pyrimidines Showing Magnetic Interactions"Acta Crystallographica Section B. 57. 772-779 (2001)

[Publications] M.Mito 他5名: "Pressure Effects of Genuine Organic Crystalline Ferromagnet Possessing Intermolecular Contacts between Nitroxide Oxygen and ..."Chemical Physics Letters. 333. 69-75 (2001)

[Publications] T.Suzuki 他8名: "Single-Component Organic Semiconductors Based on Novel Radicals that Exhibit Electrochemical Amphotericity : Preparation, Crystal..."Journal of Organic Chemistry. 66. 216-224 (2001)

[Publications] T.Katayama 他2名: "Novel Organic-Inorganic Molecular Assembiy : s Copper(I)and Copper(II)Mixed-Valent Cluster with Bromide Bridges and ..."Inorganic Chimica Acta. 329. 31-35 (2002)

[Publications] T.Nogami 他3名: "Synthesis and Properties of New Oxygen-Corntaning Fulvalene Derivatives : Dibenzo-and Dinaphthotetraoxafulvalenes and ..."Synthetic Metals. 120. 755-756 (2001)

[Publications] J.Omata, 他4名: "Radical-Copper Hexanuclear Arrays Showing Ferrpmagnetic Interactions"Polyhedron. 20. 1557-1591 (2001)

[Publications] T.Miyake, 他4名: "Ferromagnetic S=1 Chain Formed by a Square Ni_2S_2Motif in Ni(qt)2(qt=Quinoline-8-thiolate). Magnetic Properties of Related..."Polyhedron. 20. 1551-1555 (2001)

[Publications] T.Ishida, 他4名: "Zero-Field Muon Spin Rotation Study on TEMPO-Based Magnets, Ar-CH=TEMPO"Polyhedron. 20. 1545-1549 (2001)

[Publications] S.Ohira, 他6名: "Anomalous Magnetism in ~Organic Radical Ferromagnets, 4-Arylmethyleneamino-2, 2, 6, 6-tetramethylpiperidin-yloxyl just above..."Polyhedron. 20. 772-779 (2001)

[Publications] J.Omata, 他4名: "Radical-Copper Macrocycles and Related Compounds"Molecular Crystals and Liquid Crystals. (印刷中). (2002)

[Publications] T.Kusaka, 他4名: "Magnetic Phase Transition of Fe^<II>, Co^<II>, and Ni^<II> Complexes Bridged by Pyrimidine and Dicyanamide"Molecular Crystals and Liquid Crystals. (印刷中). (2002)

[Publications] M.Seino, 他3名: "Magnetic Properties of 9, 9-Disubstituted 9, 10-dihydroacridine-10-yloxyls"Synthetic Metals. (印刷中). (2002)

[Publications] T.Matsuyama, 他3名: "Hybrid Magnetic Solids of Radical-Substituted Heteroaromatic Compounds with Metal Halides"Synthetic Metals. (印刷中). (2002)

[Publications] T.Kusaka, 他2名: "Solvated Magnets of F_e[N(CN)2](pyrimidine) : Transition Phenomena Tuned by Guests"Molecular Crystals and Liquid Crystals. (印刷中). (2002)

[Publications] T.Ise, 他2名: "First Isolation and Characterization of an HIN Complex, C_dCl_2(HIN)4(HIN=4, 4, 5, 5-Tetramethylimidazolin-1-oxyl)"Molecular Crystals and Liquid Crystals. (印刷中). (2002)

石田尚行電気通信大学, 電気通信学部, 助教授 (00232306)