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 °C. MoOPcI3
crystallizes in space group Cmcm (No. 63) of the orthorhombic system with a = 14.441(3) Å, b = 15.194(3) Å,
c = 14.085(3) Å, and Z = 2. The crystals of MoOPcI3 are built up from separate units of MoOPc+ and I3-,
forming linear aggregates. The I3- ions have been also detected by Raman spectroscopy. The magnetic susceptibility
measurement versus temperature shows typical Curie−Weiss behavior. The effective magnetic moment (μeff =
1.72 μB) 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 (d1). The temperature dependence of the conductivity of
MoOPcI3 shows its metallic-like character (dσ/dT < 0). At room temperature the conductivity equals (3.5−4) ×
10-2 Ω-1 cm-1. The charge transport proceeds mainly along linear (MoOPcI3)n aggregates.