Preparation, Crystal Structure, and Solid State Properties of Highly Conductive (Phthalocyaninato)platinum Radical Salts: PtPc(ClO4)0.5and PtPc(AsF6)x
作者： Hideo Yamakado , Kyuya Yakushi , Nobuhiro Kosugi , Haruo Kuroda , Atsushi Kawamoto
DOI: 10.1246/BCSJ.62.2267
关键词: X-ray photoelectron spectroscopy 、 Tetragonal crystal system 、 Crystallography 、 Chemistry 、 Lattice constant 、 Stereochemistry 、 Metal 、 Platinum 、 Partial oxidation 、 Electrochemistry 、 Crystal structure 、 General chemistry
摘要: New conducting salts of (phthalocyaninato)platinum (PtPc), PtPc(ClO4)0.5 and PtPc(AsF6)x, were prepared by electrochemical oxidation. A crystal belongs to a tetragonal system with space group P4⁄mcc, the lattice constants being a=14.062(1) A, c=6.510(1) Z=2. They are metallic at least down 120 K, room-temperature conductivity σ=102–103 S cm−1. XPS indicates that conduction pathway is located mainly ligand chain due partial oxidation ligand-centered HOMO. ESR experiments have also strongly supported this conclusion. The bandwidth band has been estimated be 1.2 eV from plasma frequency, hωp=0.87 eV, which obtained polarized reflectance spectrum.
csj.jp参考文章(22)
Michael Y. Ogawa, Jens Martinsen, Sharon M. Palmer, Judith L. Stanton, Jiro Tanaka, Richard L. Greene, Brian M. Hoffman, James A. Ibers, Cu(pc)I: A Molecular Metal With A One-dimensional Array of Local Moments Embedded In A “Fermi Sea” of Charge Carriers Journal of the American Chemical Society. ,vol. 109, pp. 1115- 1121 ,(1987) , 10.1021/JA00238A021
Jens Martinsen, Sharon M. Palmer, Jiro Tanaka, Richard C. Greene, Brian M. Hoffman, Nickel phthalocyanine iodide: A highly-one-dimensional low-temperature molecular metal Physical Review B. ,vol. 30, pp. 6269- 6276 ,(1984) , 10.1103/PHYSREVB.30.6269
T. Inabe, T.J. Marks, R.L. Burton, J.W. Lyding, W.J. McCarthy, C.R. Kannewurf, G.M. Reisner, F.H. Herbstein, Highly conductive metallophthalocyanine assemblies. Structure, charge transport, and anisotropy in the metal-free molecular metal H2(Pc)I Solid State Communications. ,vol. 54, pp. 501- 504 ,(1985) , 10.1016/0038-1098(85)90656-8
K. Yakushi, H. Yamakado, M. Yoshitake, N. Kosugi, H. Kuroda, A. Kawamoto, J. Tanaka, T. Sugano, M. Kinoshita, S. Hino, Preparation and characterization of the cation radical salts of phthalocyanine and tetrabenzoporphyrin Synthetic Metals. ,vol. 29, pp. 95- 102 ,(1989) , 10.1016/0379-6779(89)90885-0
Tamotsu Inabe, Shuhei Nakamura, Wen Bin Liang, Tobin J. Marks, Robert L. Burton, Carl R. Kannewurf, Kenichi Imaeda, Highly conductive metallomacrocyclic assemblies: synthesis via electrocrystallization and single-crystal properties of a phthalocyanine molecular metal without halogen counterions Journal of the American Chemical Society. ,vol. 107, pp. 7224- 7226 ,(1985) , 10.1021/JA00310A103
Yasushi Iyechika, Kyuya Yakushi, Haruo Kuroda, Temperature dependence of the visible absorption band of Cu-phthalocyanine single crystal Chemical Physics. ,vol. 87, pp. 101- 107 ,(1984) , 10.1016/0301-0104(84)85143-5
M. Almeida, M.G. Kanatzidis, L.M. Tonge, T.J. Marks, H.O. Marcy, W.J. McCarthy, C.R. Kannewurf, Unusual band-filling and counterion ordering effects in a phthalocyanine molecular metal. Single crystal studies of Ni(Pc) (C104)y Solid State Communications. ,vol. 63, pp. 457- 461 ,(1987) , 10.1016/0038-1098(87)90270-5
Kyuya Yakushi, Hideo Yamakado, Michiko Yoshitake, Nobuhiro Kosugi, Haruo Kuroda, Tadashi Sugano, Minoru Kinoshita, Atsushi Kawamoto, Jiro Tanaka, Electrochemical Preparation and Characterization of the Radical Salts of (Phthalocyaninato)nickel, NiPc(SbF6)0.5, and NiPc(AsF6)0.5 Bulletin of the Chemical Society of Japan. ,vol. 62, pp. 687- 696 ,(1989) , 10.1246/BCSJ.62.687
Jens Martinsen, Laurel J. Pace, Terry E. Phillips, Brian M. Hoffman, James A. Ibers, Tetrabenzoporphyrinato)nickel(II) Iodide. A Doubly Mixed Valence Molecular Conductor Journal of the American Chemical Society. ,vol. 104, pp. 83- 91 ,(1982) , 10.1021/JA00365A018
R. J. Elliott, Theory of the Effect of Spin-Orbit Coupling on Magnetic Resonance in Some Semiconductors Physical Review. ,vol. 96, pp. 266- 279 ,(1954) , 10.1103/PHYSREV.96.266