Structure and electrical and magnetic properties of (PTMA)x[M(Pc)(CN)2]•y(solvent) (PTMA=phenyltrimethylammonium and [M(Pc)(CN)2]=dicyano(phthalocyaninato)MIII with M=Co and Fe).: Partial oxidation by partial solvent occupation of the cationic site

Electrochemical oxidation of PTMA[M-III(Pc)(CN)(2)] (PTMA=phenyltrimethylammonium, Pc=phthalocyaninato, and M=Co or Fe) gives partially oxidized salts (PTMA)(x)[M-III(Pc)(CN)(2)].y(solvent) (solvent=acetonitrile or acetone). The obtained crystals in which the solvent molecules partially occupy the cationic sites are isomorphous regardless of M and solvent. They are highly conducting and metallic behavior is observed in the conductivity and thermoelectric power measurements. In contrast to the Pauli-like behavior of the Co-III salt, Curie-like behavior with an anomaly due to antiferromagnetic interactions was observed for the Fe-III salt in magnetic susceptibility measurements. The existence of local magnetic moments in the Fe-III salt leads to a significant influence on the transport properties, suggesting the existence of pi -d interactions in this system.