1999 Fiscal Year Annual Research Report

金属フタロシアニン導体を主とするπ-d電子系の研究

Research Project

Project/Area Number	09440244
Research Institution	Okazaki National Research Institutes
Principal Investigator	薬師久弥岡崎国立共同研究機構, 分子科学研究所, 教授 (20011695)
Co-Investigator(Kenkyū-buntansha)	山本薫岡崎国立共同研究機構, 分子科学研究所, 助手 (90321603)
Keywords	フタロシアニン導体 / 偏光反射分光 / ラマン分光 / 一次元有機導体 / 金属絶縁体転移 / 電荷分離 / DMTSA / BEDO-TTF
Research Abstract	1.フタロシアニン導体の混晶Ni_xCo_<1-x>Pc(AsF_6)_<0.5>)について偏光反射分光、ラマン分光、ESR、磁化率の測定を行なった。Coを極わずか含む混晶のESRにおいてCoの超微細構造を見出した。このことより混晶における局在スピンはCo3d_z^2軌道に局在していることが明らかになった。CoPc(AsF_6)_<0.5>とNiPc(AsF_6)_<0.5>の反射率の比較から、CoPc(AsF_6)_<0.5>の伝導バンドにはCo3d_z^2軌道も関わっていることを明らかにし、バンド構造の模型を提出した.。このバンド模型は混晶で観測されるフォノンの共鳴効果も説明することができる。 2.一次元有機導体DMTSA-BF_4とDMTTA-BF_4の反射率の比較から、DMTSA-BF_4におけるオンサイトクーロンエネルギーが異常に小さく見えることを実験的に示した。このことがDMTSA-BF_4の金属性の原因になっていると考える。 3.溶媒分子を含み狭いバンド幅を持つ分子導体(BEDT-ATD)_2X(solvent)(X=PF_6,AsF_6,BF_4;solvent=THF,DHF,DO)の反射率の測定と低温構造の決定を行なった。低温では溶媒分子が部分的に配向するが、金属絶縁体転移には直接関与していないことを明らかにした。 4.結晶学的に非等価な分子をもつEt_4N(DMTCNQ)_2の反射率とラマンスペクトルを測定し、平均価数-0.5のDMTCNQは-0.4と-0.6のように電荷分離が起きていることを明らかにし、この原因をマーデルングエネルギーの計算により明らかにした。 5.2次元的な有機導体(BEDO-TTF)_2C1(H_20)_3の単結晶の反射スペクトルに異常な光吸収ピークを見出だし、これがプラズモンであることを理論的にも証明した.正反射分光法によるプラズモンの観測はこの研究がはじめてである。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] Mikio Uruichi: "Spectroscopic Study of Narrow-Band Metal (BEDT-ATD)_2PF_6(THF) without Dimerized Structure"J. Phys. Soc. Jpn.,. 68. 531-538 (1999)
[Publications] J. Ouyang: "Low-Energy Electronic Transition in Organic metal, DMTSA-BF_4"Solid State Commun. 110. 63-68 (1999)
[Publications] Kosaburo Goto: "A Stable Neutral Hydrocarbon Radical : Synthesis, Crystal Structure, and Physical Properties of 2,5,8-Tri-tert-butyl-phenalenyl"J. Am. Chem. Soc.. 121. 1619-1620 (1999)
[Publications] K. Yakushi: "Metallic properties of 1:1 Charge-Transfer Salt DMTSA-BF_4"Synthetic Metals. 103. 2208-2209 (1999)
[Publications] J. Ouyang: "Band Structure of (BDT-TTP)_2X (X=SbF_<6'> AsF_<6'>ClO_4) Studied by Reflection Spectroscopy"Synthetic Metals. 103. 2207-2207 (1999)
[Publications] M. Uruichi: "Temperature-dependent Reflection Spectra of Metallic (BEDT-ATD)_2X(THF) (X=PF_<6'> AsF_6)"Synthetic Metals. 103. 2206-2206 (1999)
[Publications] Y. Yonehara: "Optical Spectra of Phthalocyanine Salts"Synthetic Metals. 103. 2214-2215 (1999)
[Publications] M. Inokuchi: "Optical Properties of α'-(BEDT-TTF)_2IBr_2"Synthetic Metals. 103. 2101-2102 (1999)
[Publications] C. Yang: "BEDT-TTF being inserted into a layered MnPS_3"Synthetic Metals. 102. 1482-1482 (1999)
[Publications] L. Martin: "Synthesis, crystal structure and properties of the semiconducting molecular charge-transfer salt (bedt-ttf)_2Ge(C_2O_4)_3 ・ PhCN [bedt-ttf=bis(ethylenedithio)tetrathiafulvalene]"J. Mater. Chem.. 9. 2731-2736 (1999)
[Publications] J. Ouyang: "Spectroscopic Study of Isostructural Charge-Transfer Salts : Non-metallic DMTTA-BF_4 and Metallic DMTSA-BF_4"J. Phys. Soc. Jpn.. 68. 3708-3716 (1999)
[Publications] Kyuya Yakushi: "Phase Transition in Narrow-band Organic Metals (BEDT-ATD)_2X(solvent) (X=PF_<6'> AsF_<6'> BF_4 ; solvent=THF, DHF, DO)"Synthetic Metals. (in press).
[Publications] C. Nakano: "Estimation of the Site-Energy difference In the crystal of Et_4N(DMTCNQ)_2"Solid State Commun.. 113. 677-682 (2000)
[Publications] Olga Drozdova: "Determination of the Charge on BEDO-TTF in its Complexed by Raman Spectroscopy"J. Am. Chem. Soc. , to be published..
[Publications] K. Yakushi: "Observation of Plasmons by Normal-incidence Reflectivity in Two-dimensional Organic Metals"Phys. Rev. B, in press..
[Publications] K. Yakushi: "Spectroscopic Studies of Solid Phthalocyanines and their Charge-transfer Salts"J. Porphyrin and Phthalocyanine, in press,..
[Publications] K. Takeda: "Pressure-induced insulator-to-metal-to-insulator transitions in one-dimensional bis-(dimethylglyoximato)platinum(II), Pt(dmg)_2"Chemistry of Materials, in press..
[Publications] K. Takeda: "Structural, electrical and optical studies of one-dimensional bis(1,2-benzoquinone-dioximato)M(II)(M=Pd and Pt), M(bqd)_2 at high pressures"Rev. High Pressure Sci. Technol., in press..

1999 Fiscal Year Annual Research Report

金属フタロシアニン導体を主とするπ-d電子系の研究

Principal Investigator

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

Research Products

[Publications] Mikio Uruichi: "Spectroscopic Study of Narrow-Band Metal (BEDT-ATD)_2PF_6(THF) without Dimerized Structure"J. Phys. Soc. Jpn.,. 68. 531-538 (1999)

[Publications] J. Ouyang: "Low-Energy Electronic Transition in Organic metal, DMTSA-BF_4"Solid State Commun. 110. 63-68 (1999)

[Publications] Kosaburo Goto: "A Stable Neutral Hydrocarbon Radical : Synthesis, Crystal Structure, and Physical Properties of 2,5,8-Tri-tert-butyl-phenalenyl"J. Am. Chem. Soc.. 121. 1619-1620 (1999)

[Publications] K. Yakushi: "Metallic properties of 1:1 Charge-Transfer Salt DMTSA-BF_4"Synthetic Metals. 103. 2208-2209 (1999)

[Publications] J. Ouyang: "Band Structure of (BDT-TTP)_2X (X=SbF_<6'> AsF_<6'>ClO_4) Studied by Reflection Spectroscopy"Synthetic Metals. 103. 2207-2207 (1999)

[Publications] M. Uruichi: "Temperature-dependent Reflection Spectra of Metallic (BEDT-ATD)_2X(THF) (X=PF_<6'> AsF_6)"Synthetic Metals. 103. 2206-2206 (1999)

[Publications] Y. Yonehara: "Optical Spectra of Phthalocyanine Salts"Synthetic Metals. 103. 2214-2215 (1999)

[Publications] M. Inokuchi: "Optical Properties of α'-(BEDT-TTF)_2IBr_2"Synthetic Metals. 103. 2101-2102 (1999)

[Publications] C. Yang: "BEDT-TTF being inserted into a layered MnPS_3"Synthetic Metals. 102. 1482-1482 (1999)

[Publications] L. Martin: "Synthesis, crystal structure and properties of the semiconducting molecular charge-transfer salt (bedt-ttf)_2Ge(C_2O_4)_3 ・ PhCN [bedt-ttf=bis(ethylenedithio)tetrathiafulvalene]"J. Mater. Chem.. 9. 2731-2736 (1999)

[Publications] J. Ouyang: "Spectroscopic Study of Isostructural Charge-Transfer Salts : Non-metallic DMTTA-BF_4 and Metallic DMTSA-BF_4"J. Phys. Soc. Jpn.. 68. 3708-3716 (1999)

[Publications] Kyuya Yakushi: "Phase Transition in Narrow-band Organic Metals (BEDT-ATD)_2X(solvent) (X=PF_<6'> AsF_<6'> BF_4 ; solvent=THF, DHF, DO)"Synthetic Metals. (in press).

[Publications] C. Nakano: "Estimation of the Site-Energy difference In the crystal of Et_4N(DMTCNQ)_2"Solid State Commun.. 113. 677-682 (2000)

[Publications] Olga Drozdova: "Determination of the Charge on BEDO-TTF in its Complexed by Raman Spectroscopy"J. Am. Chem. Soc. , to be published..

[Publications] K. Yakushi: "Observation of Plasmons by Normal-incidence Reflectivity in Two-dimensional Organic Metals"Phys. Rev. B, in press..

[Publications] K. Yakushi: "Spectroscopic Studies of Solid Phthalocyanines and their Charge-transfer Salts"J. Porphyrin and Phthalocyanine, in press,..

[Publications] K. Takeda: "Pressure-induced insulator-to-metal-to-insulator transitions in one-dimensional bis-(dimethylglyoximato)platinum(II), Pt(dmg)_2"Chemistry of Materials, in press..

[Publications] K. Takeda: "Structural, electrical and optical studies of one-dimensional bis(1,2-benzoquinone-dioximato)M(II)(M=Pd and Pt), M(bqd)_2 at high pressures"Rev. High Pressure Sci. Technol., in press..

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