1993 Fiscal Year Annual Research Report

分子磁性発現とその機構

Research Project

Project/Area Number	04242103
Research Institution	The University of Tokyo
Principal Investigator	木下實東京大学, 物性研究所, 教授 (40011530)
Co-Investigator(Kenkyū-buntansha)	百瀬孝昌京都大学, 理学部, 講師 (10200354) 阿波賀邦夫東京大学, 教養学部, 助教授 (10202772) 加藤礼三東京大学, 物性研究所, 助教授 (80169531) 工位武治大阪市立大学, 理学部, 教授 (10117955) 榎敏明東京工業大学, 理学部, 教授 (10113424)
Keywords	分子磁性 / 有機高スピン分子 / 有機強磁性 / 反強磁性 / 伝導性分子錯体 / 磁気相互作用 / スピン分極 / 伝導性と磁性
Research Abstract	高スピン分子の関係では,前年度に引き続き2次元的に広がったπ電子軌道をもつ分子として25重項カルベンオリゴマーの合成を進め、前駆体のポリヒドラゾン化合物迄の合成ルートを確立した。また、分子内フラストレーションの期待される系、室温でも安定な高スピン分子など複雑な電子・スピン構造の解明を行っている。AO2班と共同でCOPNA樹脂の磁性についても研究を進め、脱水素COPNA樹脂においてスピングラス的な挙動を認めた。分子内フラストレーションのあるtris(4-phenylmethylene)amineは、上記研究で基底三重項であるが、これの陰イオンでは4重項が、また陽イオンでは四および六重項が観測されている。今後温度変化の測定などから基底状態を決定する必要がある。分子性錯体の研究では、昨年度(BEDT-TTF)_6Cu_2Br_8で反強磁性体が得られたが、その磁気異方性を調べ、容易軸がb軸であること、小さい異方性磁場は主として双極子-双極子相互作用によって説明されることが示唆された。一方、「重い電子」状態にある可能性が指摘されている混合原子価銅錯体(DMe-DCNQI)_2Cu系については、種々の選択的重水素試料を用いて、電気抵抗、結晶構造、比熱、磁化率、磁気抵抗、NMR等を共同研究により調べ、磁性に関しては絶縁相における反強磁性転移に伴う自発磁化の発生の詳細を明らかにし、またド・ハース・ファン・アルフェン効果により三次元的なフェルミ面をもつことを示した。強磁性体になるp-NPNNについては、班内の共同研究により加圧によりTcが低下することを見いだし、これは強磁性発現機構を調べる上で重要な手がかりになる。その他ニトロニルニトロキシド系のラジカルでは,ビラジカル、トリラジカルにおいて分子内および分子間相互作用の競合による特異な磁性がほぼ解明され、p-methylpyridinium誘導体で反強磁性カゴメ格子という非常に珍しい結晶が見つかり、その磁性を中心とした諸物性の解明が待たれる。

Research Products

(49 results)

All Other

All Publications (49 results)

[Publications] M.Kinoshita: "Ferromagnetism in organic radical crystal" Mol.Cryst.Liq.Cryst.232. 1-12 (1993)
[Publications] M.Tamura: "Magnetic properties of phenyl nitronyl nitroxides" Mol.Cryst.Liq.Cryst.232. 45-52 (1993)
[Publications] D.Shiomi: "Magnetic energy gap in the crystal of an organic biradical,m-BNN:m-Phenylene bis(α-nitronyl nitroxide)" Mol.Cryst.Liq.Cryst.232. 109-116 (1993)
[Publications] L.P.Le: "Searching spontaneous magnetic order by SR in an organic ferromagnet-- β-phase p-NPNN" Chem.Phys.Lett.206. 405-408 (1993)
[Publications] D.Shiomi: "Novel magnetic interactions in organic polyradical crystals based on nitronyl nitroxide" Synth.Metals. 56. 3279-3284 (1993)
[Publications] K.Nozawa: "Magnetic properties and crystal structures of some nitronyl nitroxide derivatives" Synth.Metals. 56. 3323-3326 (1993)
[Publications] M.Kinoshita: "Bulk ferromagnetism of the crystal of the organic radical,p-NPNN" Synth.Metals. 56. 3285-3290 (1993)
[Publications] M.Tamura: "Weak ferromagnetism and magnetic anisotropy in the Cu salt of fully deuterated DMe-DCNQI,(DMe-DCNQI-d_8)_2Cu" J.Phys.Soc.Japan. 62. 1470-1473 (1993)
[Publications] M.Tamura: "Weak ferromagnetism in (DBr-DCNQI)_2Cu(DBr-DCNQI=2,5-di-bromo-N,N'-dicyanoquinonediimine)" J.Phys.Soc.Japan. 63. 425-428 (1994)
[Publications] M.Tamura: "Magnetic study of the metal-insulator-metal transitions in (DMe-DCNQI-α,α'-d_2)_2Cu." J.Phys.Soc.Japan. 63. 429-432 (1994)
[Publications] T.Enoki: "Solid state properties of charge transfer complexes of TTF derivatives with 3d-transition metal halides" Mol.Cryst.Liq.Cryst.233. 325-334 (1993)
[Publications] K.Suzuki: "Phase transitions and magnetic properties of an organic conductor (BEDT-TTF)_6Cu_2Br_6 with mixed valence Cu ions" Synth.Metals. 56. 1741-1746 (1993)
[Publications] K.Suzuki: "Conduction mechanism and two-dimensional magnetism in incommensurate layered compounds (RES)_xMS_2(RE=Rare…" Synth.Metals. 56. 2191-2196 (1993)
[Publications] A.Nakayama: "Magnetic properties of activated carbon fibers" Synth.Metals. 57. 3736-3741 (1993)
[Publications] H.Sato: "Effects of alkali substitution and pressure on the charge-density wave transition of two-dimensional metal K_3Cu_8S_6" J.Phys.Soc.Japan. 62. 647-658 (1993)
[Publications] S.L.di Vittorio: "ESR study of activated carbon fibers:Preliminary results" J.Mater.Res.8. 2282-2287 (1993)
[Publications] K.Suzuki: "Electronic properties and valence state of Sm in (SmS)_<1.19>-TaS_2" Phys.Rev.B48. 11077-11085 (1993)
[Publications] K.Suzuki: "Variety of magnetism in incommensurate misfit layered compounds (RES)_xTS_2(RE=rare earths,T=Ta,V,Ti,Cr)" Japanese J.Appl.Phys.suppl.32-33. 341-343 (1993)
[Publications] K.Suzuki: "Electronic structures of incommensurate layered compounds (MS)_xTaS_2(M=rare earths,Pb,Sn)" Mol.Cryst.Liq.Cryst.(in press).
[Publications] T.Kondo: "Magnetism in incommensurate layer compounds (RES)_xVS_2(RE=rare earths)" Mol.Cryst.Liq.Cryst.(in press).
[Publications] T.Ishii: "Electronic structure and transport properties of AuCl_3-GIC" Mol.Cryst.Liq.Cryst.(in press).
[Publications] T.Takui: "Organic high-spin state ENDOR/TRIPLE spectroscopy:Spin and molecular structural studies of models for…" Bull.Magn.Reson.15. 120 (1993)
[Publications] K.Furukawa: "Molecular design,synthesis,and electron spin resonance detection of a ground-state tridecet(S=6) hydrocarbon as…" Bull.Magn.Reson.15. 220 (1993)
[Publications] Y.Teki: "Role of the spin correlation and weakly interacting model for the spin alignment in organic high-spin molecules" Mol.Cryst.Liq.Cryst.232. 261-270 (1993)
[Publications] K.Sato: "Spin polarization effect in organic high-spin molecules as studied by single crystal ESR and ^1H-ENDOR spectroscopies" Mol.Cryst.Liq.Cryst.232. 353-360 (1993)
[Publications] K.Furukawa: "Molecular design,synthesis,and electron spin resonance detection of a ground-state tridecet(S=6) hydrocarbon as…" Mol.Cryst.Liq.Cryst.232. 251-260 (1993)
[Publications] Y.Teki: "Magnetic behavior of (N-arylthio)-2,4,6-triphenylanilino radical crystals" Mol.Cryst.Liq.Cryst.233. 119-126 (1993)
[Publications] Y.Miura: "Synthesis of nitronyl nitroxide and nitroxide polyradicals and their magnetic characterization" Mol.Cryst.Liq.Cryst.232. 135-142 (1993)
[Publications] Y.Teki: "Novel organic ions of high-spin states" Mol.Cryst.Liq.Cryst.232. 271-288 (1993)
[Publications] T.Takui: "Unusually large negative spin polarization of hetero-spin composite high-spin carbenes as models for purely…" Mol.Cryst.Liq.Cryst.232. 343-352 (1993)
[Publications] Y.Miura: "Synthesis and magnetic characterization of poly(1,3-phenylenethylene) with pendant nitronyl nitroxide radicals" Macromolecules. 26. 3698-3701 (1993)
[Publications] Y.Miura: "Magnetic and optical characterization of poly(ethynylbenzene) with pendant nitroxide radicals" Macromolecules. 26. 6673-6675 (1993)
[Publications] Y.Teki: "Topology and spin alignment in a novel organic high-spin molecule,biphenyl-3,4'-bis(phenylmethylene) as studied…" J.Am.Chem.Soc.(in press).
[Publications] R.Kato: "Preparation and physical properties of an alloyed (DMe-DCNQI)_2Cu with fully deuterated DMe-DCNQ(DMe-DCNQI" Solid State Commun.85. 831-835 (1993)
[Publications] H.Sawa: "Novel electronic states of partially deuterated (DMe-DCNQI)_2Cu" J.Phys.Soc.Japan. 62. 2224-2228 (1993)
[Publications] S.Aonuma: "Synthesis of DMe-DCNQI-d_7 and deuterium-induced metal-insulator transition of (DMe-DCNQI-d_7)_2Cu" Synth.Met.58. 29-37 (1993)
[Publications] R.Kato: "Metallic behavior induced by Li-doping in DCNQI-Cu System" Synth.Met.56. 1864-1869 (1993)
[Publications] R.Kato: "Preparation and physical properties of an alloyed (DMe-DCNQI)_2Cu with fully deuterated DMe-DCNQI" Solid State Commun.85. 831-835 (1993)
[Publications] S.Aonuma: "Giant metal-insulator-metal transition induced by selective deuteration of the molecular conductor,(DMe-" Chem.Lett.513-516 (1993)
[Publications] K.Ishida: "Cu NMR study of the organic conductor (DMe-DCNQI)_2Cu" Phsica B. 186-188. 1059-1061 (1993)
[Publications] H.Kobayashi: "Evidence for reentrant structural-phase transition in DCNQI-Cu system" J.Am.Chem.Soc.117. 7870-7871 (1993)
[Publications] I.H.Inoue: "Electronic states in the valence-fluctuating organic conductors (DCNQI)2Cu(DCNQI=N,N'-dicyanoquinoediimine)" Phys.Rev.B47. 12917-12920 (1993)
[Publications] H.Kobayashi: "Mixed valency of Cu,electron-mass enhancement,and three-dimensional arrangement of magnetic sites in the organic…" Phys.Rev.B47. 3500-3510 (1993)
[Publications] S.Kagoshima: "Resistance enhancement by magnetic field in the regime of metal-insulator-metal re-entrant tansition of the alloy of…" Synthetic Metals. 61. 259-266 (1993)
[Publications] K.Awaga: "α-Nitronyl nitroxide cation radicals:Crystal engineering for the molecular based organic ferromagnetism" Mol.Cryst.Liq.Cryst.232. 69-78 (1993)
[Publications] K.Awaga: "Crystal structure and electronic state of the organic ferromagnet,nitrophenyl α-nitronyl nitroxide radical" Mol.Cryst.Liq.Cryst.232. 79-88 (1993)
[Publications] K.Awaga: "Photoelectron spectroscopic studies of an α-nitronyl nitroxide radical:Mechanism of ferromagnetic intermolecular‥" Mol.Cryst.Liq.Cryst.232. 27-34 (1993)
[Publications] A.Yamaguchi: "Crystal structures and magnetic properties of the p-methylpyridinium nitronyl nitroxide cation radical salts,…" Chem.Lett.1443-1446 (1993)
[Publications] M.Matsushita: "Novel organic ions of high-spin states.III:ESR and ^1H-ENDOR studies of a monocation of m-phenylene-…" Bull.Chem.Soc.Japan. 67. 74-85 (1994)

1993 Fiscal Year Annual Research Report

分子磁性発現とその機構

Principal Investigator

木下 實 東京大学, 物性研究所, 教授 (40011530)

Research Products

[Publications] M.Kinoshita: "Ferromagnetism in organic radical crystal" Mol.Cryst.Liq.Cryst.232. 1-12 (1993)

[Publications] M.Tamura: "Magnetic properties of phenyl nitronyl nitroxides" Mol.Cryst.Liq.Cryst.232. 45-52 (1993)

[Publications] D.Shiomi: "Magnetic energy gap in the crystal of an organic biradical,m-BNN:m-Phenylene bis(α-nitronyl nitroxide)" Mol.Cryst.Liq.Cryst.232. 109-116 (1993)

[Publications] L.P.Le: "Searching spontaneous magnetic order by SR in an organic ferromagnet-- β-phase p-NPNN" Chem.Phys.Lett.206. 405-408 (1993)

[Publications] D.Shiomi: "Novel magnetic interactions in organic polyradical crystals based on nitronyl nitroxide" Synth.Metals. 56. 3279-3284 (1993)

[Publications] K.Nozawa: "Magnetic properties and crystal structures of some nitronyl nitroxide derivatives" Synth.Metals. 56. 3323-3326 (1993)

[Publications] M.Kinoshita: "Bulk ferromagnetism of the crystal of the organic radical,p-NPNN" Synth.Metals. 56. 3285-3290 (1993)

[Publications] M.Tamura: "Weak ferromagnetism and magnetic anisotropy in the Cu salt of fully deuterated DMe-DCNQI,(DMe-DCNQI-d_8)_2Cu" J.Phys.Soc.Japan. 62. 1470-1473 (1993)

[Publications] M.Tamura: "Weak ferromagnetism in (DBr-DCNQI)_2Cu(DBr-DCNQI=2,5-di-bromo-N,N'-dicyanoquinonediimine)" J.Phys.Soc.Japan. 63. 425-428 (1994)

[Publications] M.Tamura: "Magnetic study of the metal-insulator-metal transitions in (DMe-DCNQI-α,α'-d_2)_2Cu." J.Phys.Soc.Japan. 63. 429-432 (1994)

[Publications] T.Enoki: "Solid state properties of charge transfer complexes of TTF derivatives with 3d-transition metal halides" Mol.Cryst.Liq.Cryst.233. 325-334 (1993)

[Publications] K.Suzuki: "Phase transitions and magnetic properties of an organic conductor (BEDT-TTF)_6Cu_2Br_6 with mixed valence Cu ions" Synth.Metals. 56. 1741-1746 (1993)

[Publications] K.Suzuki: "Conduction mechanism and two-dimensional magnetism in incommensurate layered compounds (RES)_xMS_2(RE=Rare…" Synth.Metals. 56. 2191-2196 (1993)

[Publications] A.Nakayama: "Magnetic properties of activated carbon fibers" Synth.Metals. 57. 3736-3741 (1993)

[Publications] H.Sato: "Effects of alkali substitution and pressure on the charge-density wave transition of two-dimensional metal K_3Cu_8S_6" J.Phys.Soc.Japan. 62. 647-658 (1993)

[Publications] S.L.di Vittorio: "ESR study of activated carbon fibers:Preliminary results" J.Mater.Res.8. 2282-2287 (1993)

[Publications] K.Suzuki: "Electronic properties and valence state of Sm in (SmS)_<1.19>-TaS_2" Phys.Rev.B48. 11077-11085 (1993)

[Publications] K.Suzuki: "Variety of magnetism in incommensurate misfit layered compounds (RES)_xTS_2(RE=rare earths,T=Ta,V,Ti,Cr)" Japanese J.Appl.Phys.suppl.32-33. 341-343 (1993)

[Publications] K.Suzuki: "Electronic structures of incommensurate layered compounds (MS)_xTaS_2(M=rare earths,Pb,Sn)" Mol.Cryst.Liq.Cryst.(in press).

[Publications] T.Kondo: "Magnetism in incommensurate layer compounds (RES)_xVS_2(RE=rare earths)" Mol.Cryst.Liq.Cryst.(in press).

[Publications] T.Ishii: "Electronic structure and transport properties of AuCl_3-GIC" Mol.Cryst.Liq.Cryst.(in press).

[Publications] T.Takui: "Organic high-spin state ENDOR/TRIPLE spectroscopy:Spin and molecular structural studies of models for…" Bull.Magn.Reson.15. 120 (1993)

[Publications] K.Furukawa: "Molecular design,synthesis,and electron spin resonance detection of a ground-state tridecet(S=6) hydrocarbon as…" Bull.Magn.Reson.15. 220 (1993)

[Publications] Y.Teki: "Role of the spin correlation and weakly interacting model for the spin alignment in organic high-spin molecules" Mol.Cryst.Liq.Cryst.232. 261-270 (1993)

[Publications] K.Sato: "Spin polarization effect in organic high-spin molecules as studied by single crystal ESR and ^1H-ENDOR spectroscopies" Mol.Cryst.Liq.Cryst.232. 353-360 (1993)

[Publications] K.Furukawa: "Molecular design,synthesis,and electron spin resonance detection of a ground-state tridecet(S=6) hydrocarbon as…" Mol.Cryst.Liq.Cryst.232. 251-260 (1993)

[Publications] Y.Teki: "Magnetic behavior of (N-arylthio)-2,4,6-triphenylanilino radical crystals" Mol.Cryst.Liq.Cryst.233. 119-126 (1993)

[Publications] Y.Miura: "Synthesis of nitronyl nitroxide and nitroxide polyradicals and their magnetic characterization" Mol.Cryst.Liq.Cryst.232. 135-142 (1993)

[Publications] Y.Teki: "Novel organic ions of high-spin states" Mol.Cryst.Liq.Cryst.232. 271-288 (1993)

[Publications] T.Takui: "Unusually large negative spin polarization of hetero-spin composite high-spin carbenes as models for purely…" Mol.Cryst.Liq.Cryst.232. 343-352 (1993)

[Publications] Y.Miura: "Synthesis and magnetic characterization of poly(1,3-phenylenethylene) with pendant nitronyl nitroxide radicals" Macromolecules. 26. 3698-3701 (1993)

[Publications] Y.Miura: "Magnetic and optical characterization of poly(ethynylbenzene) with pendant nitroxide radicals" Macromolecules. 26. 6673-6675 (1993)

[Publications] Y.Teki: "Topology and spin alignment in a novel organic high-spin molecule,biphenyl-3,4'-bis(phenylmethylene) as studied…" J.Am.Chem.Soc.(in press).

[Publications] R.Kato: "Preparation and physical properties of an alloyed (DMe-DCNQI)_2Cu with fully deuterated DMe-DCNQ(DMe-DCNQI" Solid State Commun.85. 831-835 (1993)

[Publications] H.Sawa: "Novel electronic states of partially deuterated (DMe-DCNQI)_2Cu" J.Phys.Soc.Japan. 62. 2224-2228 (1993)

[Publications] S.Aonuma: "Synthesis of DMe-DCNQI-d_7 and deuterium-induced metal-insulator transition of (DMe-DCNQI-d_7)_2Cu" Synth.Met.58. 29-37 (1993)

[Publications] R.Kato: "Metallic behavior induced by Li-doping in DCNQI-Cu System" Synth.Met.56. 1864-1869 (1993)

[Publications] R.Kato: "Preparation and physical properties of an alloyed (DMe-DCNQI)_2Cu with fully deuterated DMe-DCNQI" Solid State Commun.85. 831-835 (1993)

[Publications] S.Aonuma: "Giant metal-insulator-metal transition induced by selective deuteration of the molecular conductor,(DMe-" Chem.Lett.513-516 (1993)

[Publications] K.Ishida: "Cu NMR study of the organic conductor (DMe-DCNQI)_2Cu" Phsica B. 186-188. 1059-1061 (1993)

[Publications] H.Kobayashi: "Evidence for reentrant structural-phase transition in DCNQI-Cu system" J.Am.Chem.Soc.117. 7870-7871 (1993)

[Publications] I.H.Inoue: "Electronic states in the valence-fluctuating organic conductors (DCNQI)2Cu(DCNQI=N,N'-dicyanoquinoediimine)" Phys.Rev.B47. 12917-12920 (1993)

[Publications] H.Kobayashi: "Mixed valency of Cu,electron-mass enhancement,and three-dimensional arrangement of magnetic sites in the organic…" Phys.Rev.B47. 3500-3510 (1993)

[Publications] S.Kagoshima: "Resistance enhancement by magnetic field in the regime of metal-insulator-metal re-entrant tansition of the alloy of…" Synthetic Metals. 61. 259-266 (1993)

[Publications] K.Awaga: "α-Nitronyl nitroxide cation radicals:Crystal engineering for the molecular based organic ferromagnetism" Mol.Cryst.Liq.Cryst.232. 69-78 (1993)

[Publications] K.Awaga: "Crystal structure and electronic state of the organic ferromagnet,nitrophenyl α-nitronyl nitroxide radical" Mol.Cryst.Liq.Cryst.232. 79-88 (1993)

[Publications] K.Awaga: "Photoelectron spectroscopic studies of an α-nitronyl nitroxide radical:Mechanism of ferromagnetic intermolecular‥" Mol.Cryst.Liq.Cryst.232. 27-34 (1993)

[Publications] A.Yamaguchi: "Crystal structures and magnetic properties of the p-methylpyridinium nitronyl nitroxide cation radical salts,…" Chem.Lett.1443-1446 (1993)

[Publications] M.Matsushita: "Novel organic ions of high-spin states.III:ESR and ^1H-ENDOR studies of a monocation of m-phenylene-…" Bull.Chem.Soc.Japan. 67. 74-85 (1994)

木下實東京大学, 物性研究所, 教授 (40011530)