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1994 Fiscal Year Annual Research Report

分子磁性発現とその機構

Research Project

Project/Area Number 04242103
Research InstitutionThe 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

高スピン磁性高分子の関係では、新たにFTパルスESRによる過渡的量子スピン減衰運動法を導入した。高スピン高分子系では有効スピン量子数の増大とともに異なるスピン多重度の部分の混在するが、この方法によりこれらを分離・同定できることが示された。高スピン分子の電荷とスピン配列の研究では、七重項分子を陽イオンまたは陰イオンにすると四重項状態になること、スピン・フラストレーションがあり、基底状態が三重項の分子がイオン化により四重項状態になることなどが示された。
分子性錯体の関係では、昨年度報告した(BEDT-TTF)_6 Cu_2Br_8でESR,プロトン-NMR,高圧下の磁化率などの測定から、さらに詳しい知見を得た。新たに(BEDT-TTF)_2X(X=ICl_2,AuCl_2)の反強磁性転移を見いだし、ネ-ル温度22K(ICl_2)および28K(AuCl_2)を決め、磁気異方性などを測定した。また新規な物質として、磁性酸素分子を含むアルカリ金属-グラファイト層間化合物(C_<4n>KO_2,C_<4n>C_sO_2)を開発し、その磁性を調べている。一方、混合原子価銅錯体(DMe-DCNQI)_2Cu系では、選択的な重水素化試料を用いて種々の物性測定を行い、d電子の狭いバンドと伝導電子の相互作用に関する興味ある知見を得た。
ラジカル結晶の分野では、ニトロニルニトロキシドの2位にH,Br,I,CH_3など簡単な置換基をもつ基本骨格の誘導体の単結晶について、磁性と構造の関係が研究され、フェニル基置換でなくても強磁性相互作用が発現することが示された。また、粘土鉱物(サポナイト)の層間にラジカル陽イオンであるピリジニウムニトロニルニトロキシドを添加した層間化合物が新たに作られ、そのゲストーゲスト間、およびホストーゲスト間の磁気相互作用について知見が得られた。

  • Research Products

    (68 results)

All Other

All Publications (68 results)

  • [Publications] D.Shiomi: "Magnetic structure of the 4,4,4',4',5,5,5',5'-octamethyl-2,2'-m-phenylenebis(4,5-dihydroimidazol-1-oxyl 3-oxide)biradical-Quantum spin effect of S=1 species associated with…" Journal of.Materials Chemistry. 4. 915-920 (1994)

  • [Publications] Y.Hosokoshi: "Magnetic properties and crystal structure of the p-fluorophenyl nitronyl nitroxide radical crystal: Ferromagnetic intermolecular interaction leading to a three-dimensional network…" Journal of Materials Chemistry. 4. 1219-1226 (1994)

  • [Publications] M.Kinoshita: "Ferromagnetism of organic radical crystals." Japanese Journal of Applied Physics. 33. 5718-5733 (1994)

  • [Publications] Y.Hosokoshi: "Organic radical crystals,α-nitronyl nitroxide family: High-field magnetization study." Physica B. 201. 497-499 (1994)

  • [Publications] M.Kinoshita: "Ferro-and antiferro-magnetism in organic radical crystal." Physica B. (in press).

  • [Publications] K.Takeda: "Magnetism of the β-phase P-nitrophenyl nitronyl nitroxide crystal." Molecular Crystal and Liquid Crystal. (in press).

  • [Publications] Y.Hosokoshi: "Two-dimensional ferromagnetic intermolecular interactions in crystals of the p-cyanophenyl nitronyl nitroxide radical." Journal of Materials Chemistry. 5. 41-46 (1995)

  • [Publications] Y.Hosokoshi: "Magnetic properties and crystal structures of 2-hydro and 2-halo nitronyl nitroxide radical crystals." Synthetic Metals. (in press).

  • [Publications] K.Oshima: "Ferromagnetic resonance and nonlinear absorption in p-NPNN." Synthetic Metals. (in press).

  • [Publications] S.Uji: "Fermi surface and cyclotron mass in (DMe-DCNQI)_2Cu system." Synthetic Metals. (in press).

  • [Publications] H.Sawa: "Charge transfer and reentrant phenomenon in deuterated (DMe-DCNQI)_2Cu." Synthetic Metals. (in press).

  • [Publications] R.Kato: "Crystal structure and physical properties of molecular metal (DI-DCNQI)_2Cu (DIDCNQI=2,5-Diiodo-N,N'-dicyanoquinonediimine)." Synthetic Metals. (in press).

  • [Publications] M.Tamura: "Magnetic properties of DCNQI-Cu systems." Synthetic Metals. (in press).

  • [Publications] M.Tamura: "Enhanced magnetic susceptibility of(DI-DCNQI)_2Cu." Solid State Communications. (in press).

  • [Publications] K.Takeda: "Pressure-induced reduction of the Curie temperature of the organic ferromagnet p-NPNN" Journal of Magnetism and Magnetic Materials. 140-144 (1995)

  • [Publications] K.Takeda: "Pressure effects on intermolecular interactions of the genuine organic ferromagnet,β-phase p-NPNN." Physical Review B. in press).

  • [Publications] M.Tamura: "Week ferromagnetism in (DBr-DCNQI)_2Cu(DBr-DCNQI=2,5-dibromo-N,N'-dicyanoquinonediimine)" Journal of Physical Society of Japan. 63. 425-428 (1994)

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

  • [Publications] Y.Hosokoshi: "Magnetic interactions in the crystals of α-and β-phase of 2-hydro nitronyl nitroxide." Molecular Crystal and Liquid Crystal. (in press).

  • [Publications] M.Tamura: "(DCNQI)_2Cu: Variety of magnetism arising from pπ-d interactions." Molecular Crystal and Liquid Crystal. (in press).

  • [Publications] K.Oshima: "Ferromagnetic resonance in p-NPNN below 1K." Molecular Crystal and Liquid Crystal. (in press).

  • [Publications] K.Suzuki: "Variety of magnetism in incommensurate misfit layered compounds (RES)_XTS_2(RE=Rare Earths,T=Ta,V,Ti,Cr)" Japanese Journal Applied Physics. 32. 341-343 (1993)

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

  • [Publications] K.Matsushita: "Vector EPR studies on carbon fibers" Reports on Progress in Polymer Physics in Japan. 36. 465-468 (1993)

  • [Publications] T.Ishii: "Electronic structure and transport properties of AuCl_3-GIC" Molecular Crystals and Liquid Crystals. 245. 1-6 (1994)

  • [Publications] K.Suzuki: "Electronic structures of incommensurate layered compounds (MS)_XTaS_2(M=Rare Earths,Pb,Sn)" Molecular Crystals and Liquid Crystals. 245. 43-48 (1994)

  • [Publications] T.Kondo: "Magnetism in incommensurate layer compounds (RES)_XVS_2(RE=Rare Earths)" Molecular Crystals and Liquid Crystals. 245. 117-122 (1994)

  • [Publications] M.Ohba: "A new bimetallic ferromagnet,[Ni(en)_2]_3[Fe(CN)_6]_2・2H2O, with a rare Rope-Ladder chain structure" Journal American Chemical Society. 116. 11566-11567 (1994)

  • [Publications] T.Enoki: "Novel structure of microporous activated carbon fibers and their gas adsorption" Materials Research Society Symposium Proceedings. 349. 73-78 (1994)

  • [Publications] V.Z.Mordkovich: "Potassium-oxygen graphite intercalation compounds" Synthetic Metals. 68. 79-83 (1994)

  • [Publications] A.Nakayama: "Anomalous helium-gas-induced energy relaxation and evidence for ultra micropores in microporous carbon" Solid State Communications. 93. 323-326 (1995)

  • [Publications] R.Tsuchiya: "^1H-NMR study of magnetic anomaly in (BEDT-TTF)_3CuBr_4" Synthetic Metals. (in press).

  • [Publications] V.Z.Mordkovich: "New graphite intercalation compounds C_4KO_2 and C_8KO_2" Synthetic Metals. (in press).

  • [Publications] K.Sato: "FT pulsed EPR/transient quantum spin nutation spectroscopy applied to inorganic high-spin systems and a high-spin polymer as models for organic ferromagnets" Jounal of the Spectroscopy Society of Japan. 43. 280-291 (1994)

  • [Publications] Y.Teki: "Topology and spin alignment in novel organic high-spin molecule,bipheny1-3,4-bis(phenylmethylene),as studied by ESR and a generalized UHF Hubbard calculation" Journal of the American Chemical Society. 116. 11499-11505 (1994)

  • [Publications] T.Takui: "FT pulsed EPR/transient quantum spin nutation spectroscopy in the study of molecular-based magnetism: Application to high-spin polymers and ferromagnetic materials" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] K.Itoh: "New aspects of high-spin chemistry" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] R.Tamura: "Preparation and properties of chiral nitroxide radicals with helical crystal structure" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] A.S.Ichimura: "A single-crystal ESR study of stable dinitrenes" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] S.Nakazawa: "Electronic and molecular structures of a 2D septet-state tris(p-methoxyphenylmethylene) benzene as studied by ESR: A model for discotic high-spin assemblages" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] K.Furukawa: "An ESR and MO study of stable triplet diphenylmethylene with perpendicular conformations" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] Y.Yamaguchi: "Electronic and molecular structures of p-phenylenebis(phenylmethylene) in its thermally excited triplet state as studied by single-crystal ^1H-ENDOR" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] T.Takui: "Topological spin polarization and a VB picture of infinite model systems for organic polymer magnets in terms of electronic band calculations" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] T.Takui: "II-spin density determination of phenyl nitronyl nitroxide radicals: a liquid-phase ENDOR/TRIPLE study" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] D.Shiomi: "FT pulsed and cw EPR studies of stable molecular crystals" Molecular Crystals and Liquid Crystals. (in press).

  • [Publications] S.Uji: "Coexistence of one- and three-dimensional Fermi surface and heavy cyclotron mass in the molecular conductor(DMe-DCNQI)_2Cu" Physical Review B. 50. 15597-15601 (1994)

  • [Publications] S.Uji: "Fermi surface and absence of additional mass enhancement near the insulating phase in (DMe-DCNQI)_2Cu" Solid State Communications. 93. 203-207 (1995)

  • [Publications] R.Kato: "Unexpected isotpe effect in C^<13>-substituted(-C≡N) molecular conductor (DMe-DCNQI)_2Cu (DMe-DCNQI=2,5-dimethyl-N,N'-dicyanoquinonediimine)" Synthetic Metals. 68. 195-198 (1995)

  • [Publications] H.Sawa: "Charge transfer controlled phase transition in a molecular conductor,(DMe-DCNQI)_2Cu-Doping effect-" Journal of the Physical Society of Japan. 63. 4302-4305 (1994)

  • [Publications] Y.Kashimura: "Anomalous pressure-temperature phase diagram of the molecular conductor,(DI-DCNQI)_2Cu (DI-DCNQI)=2,5-diiodo-N,N'-dicyanoquinonediimine)" Solid State Communications. 93. 675-679 (1995)

  • [Publications] R.Kato: "Selectively deuterated molecular conductor (DMe-DCNQI)_2Cu-Phase diagram and dimensionality" Synthetic Metals. (in press).

  • [Publications] K.Hiraki: "Re-entrant phenomena of the organic conductor,DCNQI-Cu salts; observed by ^1H-NMR" Synthetic Metals. (in press).

  • [Publications] K.Hiraki: "Magnetic structure of the antiferromagnetic state of DCNQI-Cu salts" Synthetic Metals. (in press).

  • [Publications] S.Kagoshima: "Magnetic-field effects on the reentrant transition of alloy of pristine and fully deuterated (DMe-DCNQI)_2Cu" Synthetic Metals. (in press).

  • [Publications] S.Uji: "Fermi surface and cyclotron mass in (DMe-DCNQI)_2Cu" Synthetic Metals. (in press).

  • [Publications] S.Aonuma: "Selectively deuterated molecular conductor (DMe-DCNQI)_2Cu-preparation and chemical pressure effect" Synthetic Metals. (in press).

  • [Publications] H.Sawa: "Charge transfer and reentrant phenomenon in deuterated (DMe-DCNQI)_2Cu" Synthetic Metals. (in press).

  • [Publications] K.Ishida: "Cu NMR study of organic conductor DCNQI-Cu system" Synthetic Metals. (in press).

  • [Publications] Y.Nishio: "Giant peak in the specific heat of selectively deuterated (DMe-DCNQI)_2Cu" Synth. Metals. (in press).

  • [Publications] K.Awaga: "Variable magnetic interactions in an prganic radical system of(m-N-methylpyridinium α-nitronyl nitroxide)・X^-:A possible Kagome antiferromagnet" Physical Review B. 49. 3975-3981 (1994)

  • [Publications] H.Yamakado: "Structure and solid-state properties of the stable ring-oxidized conductor CoPc(AsF_6)0.5: Interaction between ring π-electrons and cobalt d-electron" Synthetic Metals. 62. 169-178 (1994)

  • [Publications] K.Awaga: "Magneto-structural correlation in a series of the iodide salts of p-N-alkylpyridinium nitronyl nitroxides: Dependence of the iodide-pyridinium ring interaction on the length of …" Journal of Materials Chemistry. 4. 1377-1385 (1994)

  • [Publications] K.Awaga: "Possible ‘re-entrant' behavior in magnetic properties of TBA[Fe(tdas)_2]complex" Inorganic Chemistry. 33. 5598-5600 (1994)

  • [Publications] W.Fujita: "Preparation and magnetic property of saponite clay intercalated with stable organic radicals" Journal of the Chemical Society, Chem.Commun.(in press).

  • [Publications] T.Okuno: "Coexistence of intermolecular ferromagnetic interaction and [NHN]^+ hydrogen bond in N-protonated m-pyridy; nitronyl nitroxide" Journal of the Chemical Society, Chem.Commun.(in press).

  • [Publications] M.Hasegawa: "EPR studies of the 2-D magnetic system in an organic cation radical salt,m-MPYNN^+・X^-" Synthetic Metals. (in press).

  • [Publications] K.Awaga: "Crystal structures and magnetic properties of (pyridinium nitronyl nitroxide)・X: Possible spin-1 Kagome antiferromagnet" Synthetic Metals. (in press).

  • [Publications] M.Matsushita: "Novel organic ions of high spin states,III: ESR and ^1H-ENDOR studies of a monocation of m-phenylenebis(phenylmethyene)" Bulletin of the Chemical Society of Japan. 67. 74-85 (1994)

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Published: 1996-04-08   Modified: 2016-04-21  

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