Spectroscopic and electrical properties of oxidized tris(dmit)vanadium anion complexes (dmit = 4,5-dimercapto-1,3-dithiole-2-thionate)

Several oxidized tris(dmit)vanadium anion complexes (dmit2− = the 4,5-dimercapto-1,3-dithiole-2- thionate anion) were prepared; [FeCp2] [V(dmit)3] (Cp− = the cyclopentadienyl anion), [Fe(MeCp)2][V(dmit)3] (MeCp− = the methylcyclopentadienyl anion), [Fe(Me5Cp)2] [V(dmit)3] (Me5Cp− = the pentamethylcyclopentadienyl anion), [NiCp2][V(dmit)3], Fe(V(dmit)3]2·3H2O, and Co(V(dmit)3]·3H2O. They behave as semiconductors with electrical conductivities of 1 × 10−7 to 1 × 10−4 S cm−1 measured for compacted pellets at 25 °C. On the basis of powder electronic reflectance, IR, ESR, and X-ray photoelectron spectra, electronic states of the complexes and interactions among the anion moieties are discussed.