Synthesis and magnetic properties of conductive nickel-dmbit complex

The partially-oxidized nickel-benzenedithiolene, (n-Bu4N)x[Ni(dmbit)2] where x=0.29 and dmbit = dimercaptobenzene isotrithione(S2C6H2CS3), has been synthesized by the chemical oxidation of the complex(x=2) with (n-Bu4N)Br3. The corrected susceptibility measured between 3K and 300K is fitted well with the Curie-Weiss law, and showed in good agreement with the calculated susceptibility, χc=χo+Cm/(T − Θ), where χo=−8.93×10−5emu/mol(Cm=1.66×10−2emuK/mol, Θ=−2.40K) stands for the temperature independent Pauli paramagnetic contribution. An X-ray absorption spectra(Ni K-edge) of the partially-oxidized salt was obtained and compared with those of the complexes(x=2, 1), in which it shows that nickel is surrounded by four sulfur atoms(R[Ni-S]=2.165Å) with a square planar geometry. The ligand-to-metal charge transfer(LMCT) probability is lowered when it is partially oxidized probably due to the ligand-oxidation.