A NEW APPROACH TO COFACIALLY ASSEMBLED PARTIALLY OXIDIZED METAL PHTHALOCYANINE LOW-DIMENSIONAL SOLIDS - SYNTHESIS, STRUCTURE, AND ELECTRICAL-CONDUCTIVITY PROPERTIES OF THE FE(IV) CONTAINING SPECIES [(PCFE)(2)C](I-3)(0.66) OBTAINED BY I-2 DOPING OF (MU-CARBIDO)BIS[PHTHALOCYANINATOIRON(IV)]

Oxidation by iodine of the Fe(IV)-phthalocyanine mu-carbido complex [PcFe]C-2 (Pc = phthalocyaninato anion) leads to the species [(PCFe)(2)C](I-3)(0.66) (I), whose structure consists of partially oxidized stacked [(PCFe)(2)C](+0.66) cations and parallel chains of I-3(-) ions. Powder X-ray diffraction patterns of I indicate isomorphism with PcNiI and other known saltlike I-2 doped linearly elongated metal phthalocyanine derivatives, though different samples having different crystalline character are obtained, Ia and Ib, depending on the medium used for the preparation, i.e. benzene or chloronaphthalene, respectively. Mossbauer, EPR, and IR spectra confirm, in both Ia and Ib, the presence of Fe(IV) and the formation of the phthalocyanine pi-cation radical, while Raman spectra give clear evidence of the presence of the totally symmetric I-3(-) anion. IR spectra show also, both for Ia and Ib, the typical broad absorption normally present for highly electrically conducting systems. Crystalline character and IR spectral features are examined in connection with the observed electrical conductivity values obtained on pressed powders, i.e (1.0 +/- 0.5) x 10(-2) Omega(-1) cm(-1) (Ia) and (0.5 +/- 0.5) Omega(-1) cm(-1) (Ib). A relationship between structure and electrical conductivity is discussed in the light of the data already reported on related systems.