Inorganic Chemistry, Vol.38, No.10, 2429-2433, 1999
Synthesis, structure, and characterization of oxomolybdenum(V) phthalocyaninato(2-) triiodide
Crystals of oxomolybdenum(V) phthalocyaninto(2-) triiodide, MoOPcI3 (Pc = C32H16N82-) have been obtained directly in the reaction of o-dicyanobenzene with molybdenum oxide under a stream of iodine at 210 degrees C. MoOPcI3 crystallizes in space group Cmcm (No. 63) of the orthorhombic system with a = 14.441(3) Angstrom, b = 15.194(3) Angstrom, c = 14.085(3) Angstrom, and Z = 2. The crystals of MoOPcI3 are built up from separate units of MoOPc+ and I3(-), forming linear aggregates. The I-3(-) ions have been also detected by Raman spectroscopy. The magnetic susceptibility measurement versus temperature shows typical Curie-Weiss behavior. The effective magnetic moment (mu(eff) = 1.72 mu B) shows one unpaired electron. A single EPR line was observed. The value of g (1.9716) indicate that the unpaired electron is localized on molybdenum cation (d(1)). The temperature dependence of the conductivity of MoOPcI3 shows its metallic-like character (d sigma/dT < 0). At room temperature the conductivity equals (3.5-4) x 10(-2) Ohm(-1) cm(-1). The charge transport proceeds mainly along linear (MoOPcI3)(n) aggregates.
Keywords:PORPHYRINIC MOLECULAR-METALS;CRYSTAL-STRUCTURE;CONDUCTIVITY;METALLOPHTHALOCYANINES;DIPHTHALOCYANINE;COMPLEXES;PRODUCTS;IODINE