科研費文献(1999)
Organic Compounds Under High Pressure
　有機物質を２種以上の分子から成る分子間化合物と１種の分子からできた単一有機分子化合物に分けた。ドナーとアクセプターの２種以上の分子からなる化合物の電気的性質は超伝導体と分子性導体に分けて文献を整理してみた。これらの研究に使われている高圧装置は銅ベリリウム製の容器で、クランプ型またはプレスと組み合わせた定加重式の装置である。高圧下の光学的研究にはダイヤモンドアンビル型の圧力発生装置が使用されている。圧力媒体にはフロリナートやメタノールーエタノール混合溶媒などの液体が用いられる。比較的静水圧性は良い物と思われる。低温、高圧下では超伝導や相転移が現れるなど多様な物性が見られているにもかかわらず、低温、高圧下の構造に関する研究はほとんど行われていない。今後は低温、高圧下のｘ線回折の研究が必要である。
　単一有機分子はその電子構造が閉殻なので大気圧下ではほとんどが絶縁体である。有機半導体の研究がはなやかなころ高圧下の電気的性質がしらべられている。１９６０年代が最も多い。最近100 GPa（１００万気圧）以上の圧力の発生が可能になり、酸素分子ですら超伝導になることが発見されている。ヨウ素や臭素も超伝導になる。ヨードアニルも約50 GPaで超伝導が見出されている。圧力の力を借りれば単一分子といえども劇的に性質を変えることがある。高い圧力が必要なためはダイヤモンドアンビル（単結晶ダイヤだけでなく焼結ダイヤも含む）を用いた高圧装置が中心的役割を果たすが、圧力媒体は固体又はサンプル自身で静水圧性は低い。ここでは電気的性質、光学的性質、構造の３つにわけた。高圧下のX線回折は高エネルギー研やSpring-8の軌道放射光を線源として用いている場合が多い。有機物質で高い圧力まで調べるには放射光は不可欠である。高圧下の単一有機分子のx線回折の研究は少し行われるようになってきたがまだ不十分である。特に単結晶の構造解析用の高圧技術の開発が重要である。
　
References

Electrical Properties
Molecular Superconductors(Molecular Complexes)
1) Hall Effect in (DMET)2I3 under Pressure,
Masayoshi Ishibashi、Keizo Murata,  Koichi Kikuchi、Kazuya Saito、Isao
Ikemoto、Keiji Kobayashi
Synthetic Metals 41-43(1991) 2167-2170
2) Hall Effect under Pressure in Low Dimensional Organic Superconductors,
Keizo Murata,  N.A.Fortune,  Toshihiro Takahashi、Koichi Kikuchi、Madoka
Tokumoto、Hiroyuki Anzai、Isao Ikemoto
The 5th Int. Conf. on High Pressure Semiconductors,
Jpn.J. Appl. Phys. Vol.32-1, 306-309. Kyoto, Aug. 18-20, 1992
3) 有機超伝導材料 ー物性理解への圧力効果研究の役割ー
Keizo Murata
高圧の科学と技術第2巻第3号（1993）206-211
4) The Electrical and optical properties of a-BETS2I3 and a-(BEDT-STF)2I3,
M. Inokuchi, H. Tajima, A. Kobayashi, H. Kuroda, R. Kato, T. Naito and H. Kobayashi,
Synthetic Metals, 55-57, 2495(1993).
5) Physical properties of (BEDT-TTF)4[Pt(C2O4)2],
H. Tajima, S. Toyoda, M. Inokuchi, H. Kuroda, H. Kobayashi,
Synthetic Metals, 55-57, 2257(1993).
5) Coexistence of superconductivity with CDW(or SDW): abbinient-pressure superconductor based on Ni(dmit)2,  a-EDT-TTF[Ni(dmit)2],
H. Tajima, M. Inokuchi, S. Ikeda, M. Arifuku, T. Naito, M. Tajima, T. Ohta, A. Kobayashi, R. Kato, H. Kobayashi, H. Kuroda,
Synthetic Metals, 70, 1035(1995).
6) k-(BEDT-TTF)2Cu[N(CN)2]Cl: Magnet and Superconductor. High Pressure and High Magnetic Field Experiment,
Yu. V. Sushko* , K. Murata, H. Ito, T. Ishiguro and G. Saito,Synth. Metals, 70 (1995) 907-910.
7).Static Magnetization Study of k-(BEDT-TTF)2Cu[N(CN)2]Cl,
Under High Pressure. Part.I.  High Magnetic Field
Yu. V. Sushko* , H.Shirakawa, and K. Murata, G. Saito,
Synth. Metals, 70 (1995) 937-938.
8) Static Magnetization Study of k-(BEDT-TTF)2Cu[N(CN)2]Cl,
Under High Pressure. Part.II.  Low Magnetic Field
Yu. V. Sushko* , H.Shirakawa, and K. Murata, G. Saito,
Synth. Metals, 70 (1995) 939-940.
9). Fermi Surface Dependence of the Hall Coefficient in Quasi-2D Molecular Conductors,
N. A. Fortune, P. J. Fons and K. Murata, Synth. Metals, 70 (1995) 1001-1004.
10) Magnetic Properties of Organic Conductor (BEDT-TTF)3CuBr4
Jun'ichi Yamaura、Kazuya Suzuki、Yoko Kaizu、Toahiaki Enoki、Keizo Murata, Gunzi Saito, J. Phys. Soc. Jpn.No.8 (1996)　pp2645-2654.
11) Hall Effect and Anomalies and Phase Transitions in the Organic
Superconductors, k-(BEDT-TTF)2Cu(NCS)2 and b-(BEDT-TTF)2I3.
Keizo Murata, J. Phys.I (France) 6(No.12)pp.1865-1873 (1996).
12) Electrical Conductivity and uppercritical magnetic field of the molecular superconductor  a-(EDT-TTF)[Ni(dmit)2],
M. Inokuchi, H. Tajima, T. Ohta, A. Kobayashi, H. Kuroda, T. Naito, A. Sato and H. Kobayashi,
Advanced Materials for Optics and Electronics, 6, 367(1996).
13) Electrical Resistivity underhigh pressure and upper critical magnetic Field of the molecular superconductor a-(BED-TTF)[Ni(dmit)],
M. Inokuchi, H. Tajima, T. Ohta, H. Kuroda, A. Kobayashi, A. Sato, T. Naito and H. Kobayashi, J. Phys. Soc. Jpn., 63, 538(1996).
14)　新しい物性を示す有機伝導体、τ型導体
Keizo Murata
文部省科研費、重点領域研究（２５３）「分子性物質における新しい電子相」分子性導体ニュース、No.4,1997年1月pp37-44.
15) NMR Investigation of Field Induced Phase of alpha-(BEDT-TTF)2I3 under ressure,
A. Shiomi, S. Yoshizaki, T. Nakamura, T. Takahashi, K. Murata,
Synth Met. 86 (1997) 1975-1976.
16) Hysteretic Magnetic State in the Organic tau-Phase Conductors,
Keizo Murata, Harukazu Yoshino, Yoshinori Tsubaki* and George C.
Papavassilioua,   Synth. Met. 94-1 (1998) 69-72.
17) A new molecular superconductor  b'-Et2Me2P[Pd(dmit)2]2,
R. Kato, Y. Kashimura, S. Aonuma, N.Hanasaki and H. Tajima,
Solid State Commun., 105, 561(1998).
18) Pressure-temperature phase diagram of a Molecular superconductor EDT-TTF[Ni(dmit)2],
H. Tajima, M. Inokuchi, H. Kuroda, A. Kobayashi, A. Sato, N. Naito and H. Kobayashi, ReV. High Pressure Sci. Technol. 7, 532(1998).
19) Hall Effect under Perssure and Phase Transitions in the Organic Superconductors, kappa-(BEDT-TTF)2Cu(NCS)2 and beta-(BEDT-TTF)2I3,
Keizo Murata, Rev. High Pressure Sci. Technol. Vol. 7 (1998) 407-411.
20) Anion-Ordering Transition in (TMTSF)2ClO4 under Pressure,
Fang Zhun GUO, Keizo MURATA, Harukazu YOSHINO, Suguru MAKI, Satoru TANAKA, Jun-ichi YAMADA, Shinユichi NAKATSUJI, Hiroyuki ANZAI
J. Phys. Soc. Jpn. 47  No. 9 (1998)3000-3002.
21) PRESSURE-TEMPERATURE PHASE DIAGRAM OF 24 K-TRANSITION OF ANION ORDERING OF (TMTSF)2ClO4F,
Zhun Guo, Keizo Murata, Harukazu Yoshino, S. Maki, S. Tanaka, J. Yamada, H. Anzai
to be published in Synth. Met.
22) RESIDUAL RESISTIVITY OF THE ORGANIC SUPERCONDUCTOR, k-(BEDT-TTF)2Cu(NCS)2 UNDER EXTREME PRESSURE,
T. Teramachi, Fang Zhun Guo, Harukazu Yoshino, N. Takeshita, N. Mori, S. Maki, S. Tanaka, J. Yamada, H. Anzai, Keizo Murata
to be published in Synth. Met.

Molecular Conductors(complexes)
1) Electrical and optical behavior of one-dimensional organic conductors at high pressure,
I. Shirotani, A. Onodera, and H. Anzai, J. Solid State Chem., 36, 246(1981).
2) Phase transitions in N-n-propylpyridinium-TCNQ2 and N-n-butylpyridinium-TCNQ2 at high pressure,
I. Shirotani, Y. Wada, S. Yoshida, T. Kajiwara, M. Murakami and S. Yoshimura,
Solid State Commun., 36, 246(1981). 
3).Low Temperature Electronic States in (DMeO-DCNQI)2Cu under Pressure,
Keizo Murata, Masayoshi Ishibashi, N.A.Fortune,Akiko Kobayashi、Reizo Kato, Hayao Kobayashi
Synthetic Metals 41-43(1991) 2148-2490
4) Structural and electronic properties of Cs[Pd(dmit)2]2,
A.E. Underhill, R.A. Clark, I. Marsden, M. Allan, R.H. Friend, H. Tajima, T. Naito, M. Tamura, H. Kuroda, A. Kobayashi, H. Kobayashi, E. Canadel, S. Ravy and J.P. Pouget, J. Phys: Condens. Matter, 3, 933(1991).
5)Electrical conductivity of a Cs2(TCNQ)3 single crystal measured at high pressures by a diamond anvil cell,
S. Matuzaki, Synth. Met., 61, 207(1993).
6).Electronic Properties of Ni(Pc)I under pressure
Keizo Murata, Norio Ohashi, Kazuhiko Murata, Julie Thompson and Brian M.
Hoffman
Synthetic Metals, 55-57 (1993) 1777-1782.
7) Synthesis, crystal structure and electrical properties of two new palladium complexes of selenium and sulfer ligands:[NMe4][Pd(C3S3Se2)2]2 and [PMe4][Pd(C3S5)2]2,
C. Faulmann, J-P Legros, P. Cassoux, J. Cornelissen, L. Brossard, M. Inokuchi, H. Tajima and M. Tokumoto,
J. Chem. Spoc. Dalton Trans., 249(1994).
8)Electrical Conductivity of One-dimensional Halogen-bridged Metal Complexes at High Pressures,
I. Shirotani, A. Kawamura, M. Yamashita, K. Toriumi, K. Kawamura and T. Yagi,
 Synthetic Metals, 64, 265-270(1994 ).
9). Low Temperature Properties of Ni(Pc)I Under Pressure,
K. Murata, M. Mori, K. Murata, J. A. Thompson, and B. Hoffman,
Synth. Metals, 71 (1995) 2297-2298.
10) Pressure-induced d-p charge transfer in one-dimensional phalocyanine conductors, NiPc(AsF6)0.5 and CoPc(AsF6)0.5,
T. Hiejima and K. Yakushi,  J. Chem. Phys., 103, 3950(1995).
11) フタロシアニン導体における圧力誘起電荷移動、
薬師久弥、米原由華子、 高圧力の科学と技術、６、１６７（１９９７）。
12)Compressibility and high-pressure electrical resitivity of one-dimensional phtalocyanine conductors:the relationship with d-p charge transfer.
T. Hiejima, K. Yakushi, T. Adachi, O. Shimomura, K. Takeda, I. Shirotani, K. Imaeda and H. Inokuchi,
Mol. Cryst. Liq. Cryst., 296, 255(1997).
13) A supermolecular cation in a electrically conducting nickel dithiolate salt, 
T. Akutagawa, T. Nakamura, T. Inabe and A. E. Underhill, 
J. Mater. Chem., 7, 183(1997).
14) High-pressure study of one-dimensional phtalocyanine conductor, NiPc(AsF6)0.5,
Y. Yonehara and K. Yakushi,  Synthetic Metals, 94, 149(1998).

Optical Properties(Complexes)
1) Low-temperature and high-pressure reflectance spectra of benzidine TCNQ charge-transfer complex,
K. Yakushi, T. Uesaka and H. Kuroda, Mol. Cryst. Liq. Cryst.,125, 353(1985).
2) Pressure dependence of the polarized reflectance spectrum of the solid carge-transfer complex, perylene-TCNQ: Estimation of microscopic parameters,
T. Ida, K, Yakushi and H. Kuroda, J. Chem. Phys., 91, 3450(1989).
3) High-pressure Optical study of partially oxidized metallophtalocyanines and metallotetrabenzo-porphyrins,
T. Ida, H. Yamakado, H. Masuda ,K. Yakushi, D. Kanazawa, H. Tajima and H. Kuroda, Mol. Cryst. Liq. Cryst., 181, 243(1990).
4) Pressure-induced phase transition of Cs2(TCNQ)2, crtstal revealed by Raman spectroscopy,
S. Matuzaki, Y. Mazushita and M. Sano, Solid State Commun., 74, 1265(1990).
5) Pressure dependence of the polarized reflectance spectrum of a solid chrge-transfer complex, perylene-hexacyanobutadiene(HCBD),
T. Ida, K. Yakushi, H. Kuroda, H. Yamochi and G. Saito,
Chem. Phys., 156, 113(1991).
6)Pressure-induced neutral-ionic phase transition in a 2:1 charge transfer crystal of Tetrathiafulvalene and Iodanil, (TTF)2IA,
S. Matsuzaki, T. hiejima and M. Sano, Solid State Commun., 82, 301(1992).
7) Optical spectra of C60 complexes at high pressures, 
S. Matuzaki, K. Hashimoto, T. Tomiku, H. Fujimoto, K. Ichimura, 
Fullerene Science and Technology, 31, 59(1995).
8) Neutral-ionic transition in TTF2Ia at high pressure,
K. Tasaki, S. Matuzaki and V.M. Yartsev, Solid State Commun.,103, 365(1997).
9) Charge transfer in C60*TMTSF*2(CS2) complex at high pressure: a Raman spectroscopic study,
G.A. Kourouklis, K.P. Meletov, J. Aravanitides, K. Papagelis, S. Ves, V.K. Dolganov, N.G. Spitsina, E.B. Yagubskii, Rev. High Pressure Sci. Technol. , 7, 733(1998).

Single Molecules
Electrical properties
1) Conductive Phthalocyanines under Very High Pressure.
 A. Onodera, N. Kawai, and T. Kobayashi,
Solid State Communications, 17, 775-778 (1975).
2) Electrical conductivity of hexaiodobenzene and tetrahalo-p-benzokinone under very high pressure,
I. Shirotani, A. Onodera, Y. Kamura, H. inokuchi and N. Kawai,
J. Solid State Chem., 18, 235(1976).
3)Insulator-to-Metal-to-Semiconductor Transitions of one-dimensional Bis(1,2-dionedioximato)Pt(II) Complexes at High Pressures,
I. Shirotani, A. Kawamura, K. Suzuki, W. Utsumi and T. Yagi,
Bull. Chem. Soc. Jpn., 64, 1607(1991).
4) Absorption Spectra and Electrical Resistivities of Bis(1,2-dionedioximato)-nickel(II) Complexes at High Pressures,
I. Shirotani, K. Suzuki, T. Suzuki, T. Yagi and M. Tanaka,
Bull. Chem. Soc. Jpn.., 65, 1078(1992).
5) Hall-effect obsevation in the new organic semiconductor bis(1,2,5 thiadiazolo)-p-quinobis(1,3-dithiole)(BTQBT),
K. Imaeda, Y. Yamashita, Y. Li, T. Mori, H. Inokuchi and M. Sano,
J. Mater. Chem., 2, 115(1992).
6)Pressure-induced Superconductivity of Iodanil,
T. Yokota, N. Takeshita, K. Shimizu, K. Amaya, A. Onodera, I. Shirotani and S. Endo, Czechoslovak J. Phys., Suppl. S2, 46, 817-818(1996).
7) 超高圧下における単一有機分子の電気伝導及び超伝導、
城谷一民、電子情報通信学会技術研究報告（有機エレクトロニクス）、９７、No. 88、２５ー３０（１９９７）。
8) Pressure Induced Superconductivity in Some Simple systems,
K. Amaya, K. Shimizu, N. Takeshita, S. Kometani, M.I. Eremets, A. Onodera, T.C. Kobayashi, T. Mizutani, M. Ishizuka, S. Endo, M. Takai, N. Hamaya and I. Shirotani, Rev. High Pressure Sci. Technol., 7, 688-693(1998).

Optical Properties(Single molecules)
1) Electrical and oprtical properties of hexaethylenetetratellurafulvalene crystals their pressure dependence,
S. Matsuzaki, H. Okumura, H. Takeuchi, T. Kyouda M. Sano, 
Synth. Met., 39, 385(1991).
2) High-Pressure FT-IR study of solid C60,
K. Aoki, H. Yamawaki, Y. Kakudate, M. Yoshida, S. Usuba, S. Fujiwara, Y. Bae, R. Malhotra, D. Lorents, J. Phys.Chem., 95, 9037(1991).
3)Pressure-sensitive Absorption Spectra of Thin Films of Bis(diphenylglyoximato)platinum(II), Pt(dpg)2: Potential Application as an Indicator of Pressure,
I. Shirotani, Y. Inagaki, W. Utsumi and T. Yagi,
J. Mater. Chem., 1, 1041-1043(1991).
4) Infrared study of phase transition and chemical reaction in tetracyanoethylene under high pressure,
H. Yamawaki, K. Aoki, Y. Kakudate, M. Yoshida, S. Usuba, S. Fujiwara,
Chem. Phys. Lett.,, 171, 183(1992).
5) Optical Properties of high-pressure phases of C60 fullerene,
M.E. Kozolov and K. Yakushi, J. Phys.: Condens. Matter, 7, L209(1995).
6) Reversible phase transition between the metastable phase of tetracyanoethylene under pressure,
H. Yamawaki, M. Sakashita, K. Aoki and K. Tekemura,
Phys. Rev., B53, 11403(1996).
7) FT-IR study of the solid state ploymerization of acetylene under pressure,
M. Sakashita, H. Yamawaki and K. Aoki, J. Phys. Chem., 100, 9943(1996).
8) IR-spectra of halogenidanil under high pressure: Metallization of Iodanil by charge transfer, 
A. Nakayama, K. Aoki and I. Shirotani,  Rev. High Pressure Sci. Technol. , 7, 529(1998).
9) Infrared study of iodanil under very high pressure
A. Nakayama, K. Aoki, Y. Matsushita and I. Shirotani
Solid state Commun., 110, 627-632(1999).

X-ray diffraction(Single Molecules)
1) The structure changes and proton transfer between O---O in the bis(dimethylglyoximato)platinum at low temperature(150K) and high pressures(2.39 and 3.14 GPa), 
M. Konno, T. Okamoto and I. Shirotani,  Acta Cryst., B45, 142(1989).
2) Exiciton-phonon coupling and pressure-induced structural phase transition in coronene crystals,
T. Yamamoto, S. Nakatani, T. Nakamura, K. Mizuno, A.H. Matsui, Y. Akahama, and H. Kawamura, Chem. Phys., 184, 247(1994).
3) X-ray diffraction study of solid acetylene under pressure,
M. Sakashita, H. Yamawaki, and K. Aoki, Rev. High Pressure Sci. Technol. , 6, 849(1996).
4) Pressure-induced structural transition of CCl4,
H. Kawamura, M. Kobayashi, Y. Yamamoto, N. Matsui and Y. Akahama,
Solid State Commun.,102, 501(1997).
5) Structural Studies on bromobenzen under high pressure, 
Y. Nishiumi, Y. Akahama, M. Kobayashi, M. Hiue, and H. Kawamura,
High Pressure Research, 16, 1(1998).
6) Phase transition of solid CF4 under high pressure,
I. Nakahata, N. Matsui, Y. Akahama, M. Kobayashi and H. Kawamura,
Rev. High Pressure Sci. Technol. , 7, 802(1998).
7) Phase relations of camphene at high pressure up to 9.5 GPa.
 K.Suito, A.Ohta, N.Sakurai, A.Onodera, M.Motoyama, and K.Yamada
 J. Chem. Phys., 109, 670-675 (1998).
8) Three-dimensionalPolymerization of Fullerite C60 under high pressure,
A.G. Lyapin, V.V. Brazhkin, S.G. Lyapin, S.V. Popova, Rev. High Pressure Sci. Technol. , 7, 811(1998).
9) Phase transformations of C70 fullerite under high pressure of 6.5-12.5 GPa and temperature 300-1830 K: comparison with C60,
V.D. Blank, S.G. Buga, N.R. Serebryana, G.A. Dubitsky, S.N. Sulyanov, Rev. High Pressure Sci. Technol. , 7, 814(1998).
10) Structural transformations in fullerite C60 under high pressure(P = 12.5 GPa) and high temperature conditions,
V.V. Brazhkin, A.G. Lyapin, S.G. Lyapin, S.V. Popoba, R.N. Voloshin, Yu.A. Antonov, E.N. Yakovlef, Rev. High Pressure Sci. Technol. , 7, 817(1998).
11) High-pressure synthesis of cyclic diphenylacetylene oligomer,
Y. Kojima, T. Matsuoka, H. Takahashi, Rev. High Pressure Sci. Technol. , 7, 829(1998).
12) Structural change of iodanil under high pressure
A. Nakayama, H. Fujihisa, K. Aoki and I. Shirotani, 
Synthetic Metals, 103, 1901-1902(1999).