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

Abstract

Electrochemical oxidation of PTMA[MIII(Pc)(CN)2] (PTMA = phenyltrimethylammonium, Pc = phthalocyaninato, and M = Co or Fe) gives partially oxidized salts (PTMA)x[MIII(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 CoIII salt, Curie-like behavior with an anomaly due to antiferromagnetic interactions was observed for the FeIII salt in magnetic susceptibility measurements. The existence of local magnetic moments in the FeIII salt leads to a significant influence on the transport properties, suggesting the existence of π–d interactions in this system.