1997 年度実績報告書

金属フタロシアニン導体を主とするπ-d電子系の研究

研究課題

研究課題/領域番号	09440244
研究種目	基盤研究(B)
研究機関	岡崎国立共同研究機構
研究代表者	薬師久弥岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)
キーワード	π-d電子系 / ニッケルフタロシアニン / コバルトフタロシアニン / 高圧 / 圧力誘起電荷移動 / 強磁性相互作用 / 電荷移動塩
研究概要	1.フタロシアニン導体NiPc(AsF_6)_<0.5>とCoPc(AsF_6)_<0.5>の粉末X線回折を高圧力下4.5GPaまで測定し、格子定数の圧力依存性とX線回折パターンからこの圧力まで構造相転移が生じてない事を明らかにした。この結果高圧力下で起こる金属イオンから配位子への電荷移動が純電子的なものである事を証明した。またNiPc(AsF_6)_<0.5>の電気抵抗と熱起電力を1GPaまでの加圧下で測定した結果、金属・絶縁体転移の温度が徐々に上昇する事が分かった。これは圧力誘起電荷移動によってニッケル鎖へ正孔がドープされ、その結果、ニッケル鎖に乱雑ポテンシャルが発生し、周辺のπ電子系に局在化を引き起こしたためである。 2.非平面の電子供与体BDNTと金属錯体イオンM(mnt)_2(M=Ni,Pd,Pt,Au)との電荷移動塩を調製し、組成、構造、電気抵抗、磁気的性質を調べた。得られた電荷移動塩は(BDNT)_2[Ni(mnt)_2)]、(BDNT)[Pd(mnt)_2)]、(BDNT)[Pt(mnt)_2]、(BDNT)[Au(mnt)_2]_2であるが、構造解析のできたBDNT[Au(mnt)_2]_2以外の電荷移動塩は粉末試料ながら高い電気伝導性(σ_<RT>=0.5-0.01Scm^<-1>)を示すが、電気抵抗の温度依存性が活性化型である。これらの電荷移動塩の中で、(BDNT)_2[Ni(mnt)_2]が20K以下で強磁性的な相互作用をもつ事を発見した。2Kまでの温度で磁化にヒステリシスは観測されず、相転移はしていない。構造が分からないので強磁性相互作用の起源はよく分からないが、ESRの実験から強磁性得相互作用を示す不対電子はNi(mnt)_2側に、電気伝導を担う電子はBDNT側にある事を明らかにした。

研究成果
(22件)

すべてその他

すべて文献書誌 (22件)

[文献書誌] J.Dong: "Characterization of the half-filled DMTSA-BF_4 by optical and magnetic measurements" Synthetic Metals. 84. 633-634 (1997)
[文献書誌] A.Otsuka: "Superconductivity in charge transfer complexes of C_<60>" Synthetic Metals. 85. 1459-1460 (1997)
[文献書誌] J.Qin: "Synthesis and Ferromagnetism of a New Intercalation Compound : Mn_<0.86>PS_3(bipy)_<0.56>" Synthetic Metals. 85. 1673-1674 (1997)
[文献書誌] V.A.Ivanov: "Electron-electron correlation with particular attention to m-BDNT-PF_6 : spin susceptibility" Synthetic Metals. 86. 2107-2108 (1997)
[文献書誌] K.Yakushi: "Pressure-Induced Charge Transfer in Phthalocyanine Conductors" Synthetic Metals. 86. 2137-2138 (1997)
[文献書誌] T.Hiejima: "Compressibility of One Dimensional Phthalocyanine Conductors,NiPc(AsF_6)_<0.5> and CoPc(AsF_6)_<0.5>" Synthetic Metals. 86. 2167-2168 (1997)
[文献書誌] T.Hiejima: "Pressure and Temperature Dependence of the Electrical Resistivity of One-dimensional Phthalocyanine Conductor,NiPc(AsF_6)_<0.5>" Synthetic Metals. 86. 2185-2186 (1997)
[文献書誌] M.E.Kozlov: "Electron-molecular vibration coupling in organic charge-transfer salts : application of spectroscopic and Hubbard models" Synthetic Metals. 86. 2177-2178 (1997)
[文献書誌] T.Manabe: "Competition between Electron-Correlation in Ni(III)and Electron-Lattice Interaction in Pd(II)-Pd(IV) in Mixed-Metal MX-Chain,Ni_<1-X>Pd_X(chxn)_2Br_3" Synthetic Metals. 86. 2233-2234 (1997)
[文献書誌] M.E.Kozlov: "Preparation and study of high-pressure phases of C_<60> fullerene" Synthetic Metals. 86. 2349-2350 (1997)
[文献書誌] H.Kajii: "Low-field microwave absroption and ESR in "conducting polymer-fullerene-alkali metal" superconductors : comparative study of various host matrices" Synthetic Metals. 86. 2351-2352 (1997)
[文献書誌] T.Hiejima: "Compressibility and high-pressure electrical resistivity of one-dimensional phthalocyanine conductors : the relationship with d-π charge transfer" Mol.Cryst.Liq.Cryst.296. 255-268 (1997)
[文献書誌] T.Yamashita: "Galvanomagnetic, Optical Properties and Ultraviolet Photoelectron Spectra of Potassium-Oxygen-Graphite Intercalation Compounds" J.Phys.Soc.Jpn.66. 158-168 (1997)
[文献書誌] M.E.Kozlov: "Spectroscopic characterization of pressure modified C_<60>" Phys.A. 64. 241-245 (1997)
[文献書誌] V.Ivanov: "Electronic structure of κ-ET_2X salts,where "ET" is bis(ethylenedithio)tetrathio) tetrathiafulvalene(BEDT-TTF)molecue" Physica C. 275. 26-36 (1997)
[文献書誌] K.Ueda: "New Spiro Donor Molecules : Bis(tetrathiafulvalenyldithio)-methane and -germane" Chem.Lett.461-462 (1997)
[文献書誌] H.Kajii: "Microwave heating effect on two Josephson-junction systems in granular PAT12-C_<60>-Rb composites : low-field microwave absorption study" Physica C. 227. 277-284 (1997)
[文献書誌] V.A.Ivanov: "Electronic Structure and Mott Transition in κ-(BEDT-TTF)_2X Salts" Physica C. 282-287. 1907-1908 (1997)
[文献書誌] M.E.Kozlov: "Spin-glass behaviour of nanocrystalline diamond intercalated with potassium" J.Phys. : Condens.Matter. 9. 8325-8332 (1997)
[文献書誌] I.L.Kogan: "New conducting composite material based on a platinum phthalocyanine(PtPc) charge transfer(CT) salt and poly-bisphenol-A-carbonate(PBC)" J.Mater.Chem.7. 2231-2234 (1997)
[文献書誌] K.Yakushi: "Pressure-Induced Charge Transfer in Phthalocyanine Conductors" High Pressure Science and Technology. 6,No.3. 167-175 (1997)
[文献書誌] M.Uruichi: "Charge-Transfer Salts of M(mnt)_2,(M=Ni,Pd,Pt,Au)with BDNT : Ferromagnetic Interaction in Conductive (BDNT)_2-[Ni(mnt)_2〕" J.Mater.Chem.8. 141-146 (1998)

1997 年度 実績報告書

金属フタロシアニン導体を主とするπ-d電子系の研究

研究代表者

薬師 久弥 岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)

研究成果

[文献書誌] J.Dong: "Characterization of the half-filled DMTSA-BF_4 by optical and magnetic measurements" Synthetic Metals. 84. 633-634 (1997)

[文献書誌] A.Otsuka: "Superconductivity in charge transfer complexes of C_<60>" Synthetic Metals. 85. 1459-1460 (1997)

[文献書誌] J.Qin: "Synthesis and Ferromagnetism of a New Intercalation Compound : Mn_<0.86>PS_3(bipy)_<0.56>" Synthetic Metals. 85. 1673-1674 (1997)

[文献書誌] V.A.Ivanov: "Electron-electron correlation with particular attention to m-BDNT-PF_6 : spin susceptibility" Synthetic Metals. 86. 2107-2108 (1997)

[文献書誌] K.Yakushi: "Pressure-Induced Charge Transfer in Phthalocyanine Conductors" Synthetic Metals. 86. 2137-2138 (1997)

[文献書誌] T.Hiejima: "Compressibility of One Dimensional Phthalocyanine Conductors,NiPc(AsF_6)_<0.5> and CoPc(AsF_6)_<0.5>" Synthetic Metals. 86. 2167-2168 (1997)

[文献書誌] T.Hiejima: "Pressure and Temperature Dependence of the Electrical Resistivity of One-dimensional Phthalocyanine Conductor,NiPc(AsF_6)_<0.5>" Synthetic Metals. 86. 2185-2186 (1997)

[文献書誌] M.E.Kozlov: "Electron-molecular vibration coupling in organic charge-transfer salts : application of spectroscopic and Hubbard models" Synthetic Metals. 86. 2177-2178 (1997)

[文献書誌] T.Manabe: "Competition between Electron-Correlation in Ni(III)and Electron-Lattice Interaction in Pd(II)-Pd(IV) in Mixed-Metal MX-Chain,Ni_<1-X>Pd_X(chxn)_2Br_3" Synthetic Metals. 86. 2233-2234 (1997)

[文献書誌] M.E.Kozlov: "Preparation and study of high-pressure phases of C_<60> fullerene" Synthetic Metals. 86. 2349-2350 (1997)

[文献書誌] H.Kajii: "Low-field microwave absroption and ESR in "conducting polymer-fullerene-alkali metal" superconductors : comparative study of various host matrices" Synthetic Metals. 86. 2351-2352 (1997)

[文献書誌] T.Hiejima: "Compressibility and high-pressure electrical resistivity of one-dimensional phthalocyanine conductors : the relationship with d-π charge transfer" Mol.Cryst.Liq.Cryst.296. 255-268 (1997)

[文献書誌] T.Yamashita: "Galvanomagnetic, Optical Properties and Ultraviolet Photoelectron Spectra of Potassium-Oxygen-Graphite Intercalation Compounds" J.Phys.Soc.Jpn.66. 158-168 (1997)

[文献書誌] M.E.Kozlov: "Spectroscopic characterization of pressure modified C_<60>" Phys.A. 64. 241-245 (1997)

[文献書誌] V.Ivanov: "Electronic structure of κ-ET_2X salts,where "ET" is bis(ethylenedithio)tetrathio) tetrathiafulvalene(BEDT-TTF)molecue" Physica C. 275. 26-36 (1997)

[文献書誌] K.Ueda: "New Spiro Donor Molecules : Bis(tetrathiafulvalenyldithio)-methane and -germane" Chem.Lett.461-462 (1997)

[文献書誌] H.Kajii: "Microwave heating effect on two Josephson-junction systems in granular PAT12-C_<60>-Rb composites : low-field microwave absorption study" Physica C. 227. 277-284 (1997)

[文献書誌] V.A.Ivanov: "Electronic Structure and Mott Transition in κ-(BEDT-TTF)_2X Salts" Physica C. 282-287. 1907-1908 (1997)

[文献書誌] M.E.Kozlov: "Spin-glass behaviour of nanocrystalline diamond intercalated with potassium" J.Phys. : Condens.Matter. 9. 8325-8332 (1997)

[文献書誌] I.L.Kogan: "New conducting composite material based on a platinum phthalocyanine(PtPc) charge transfer(CT) salt and poly-bisphenol-A-carbonate(PBC)" J.Mater.Chem.7. 2231-2234 (1997)

[文献書誌] K.Yakushi: "Pressure-Induced Charge Transfer in Phthalocyanine Conductors" High Pressure Science and Technology. 6,No.3. 167-175 (1997)

[文献書誌] M.Uruichi: "Charge-Transfer Salts of M(mnt)_2,(M=Ni,Pd,Pt,Au)with BDNT : Ferromagnetic Interaction in Conductive (BDNT)_2-[Ni(mnt)_2〕" J.Mater.Chem.8. 141-146 (1998)

1997 年度実績報告書

薬師久弥岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)