Preparation, Crystal Structure, and Solid State Properties of Highly Conductive (Phthalocyaninato)platinum Radical Salts: PtPc(ClO4)0.5 and PtPc(AsF6)x

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Abstract
New conducting salts of (phthalocyaninato)platinum (PtPc), PtPc(ClO4)0.5 and PtPc(AsF6)x, were prepared by electrochemical oxidation. A crystal of PtPc(ClO4)0.5 belongs to a tetragonal system with a space group of P4⁄mcc, the lattice constants being a=14.062(1) Å, c=6.510(1) Å, and Z=2. They are metallic at least down to 120 K, the room-temperature conductivity being σ=102–103 S cm−1. XPS indicates that the conduction pathway is located mainly at the ligand chain due to a partial oxidation of the ligand-centered HOMO. ESR experiments have also strongly supported this conclusion. The bandwidth of the ligand-centered conduction band has been estimated to be 1.2 eV from the plasma frequency, hωp=0.87 eV, which is obtained by the polarized reflectance spectrum.

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