Organoheterobimetallic cyanodithioimidocarbonates and their I2-doped products: Synthesis, characterization and conducting properties

Complexes of the type [PhHg]2[M(cdc)2], [Me2Sn][M(cdc)2], [n-Bu2Sn][M(cdc)2], [n-Bu3Sn]2[M(cdc)2] and [Ph3Sn]2[M(cdc)2] (M = Ni(II) and Cu(II); cdc2− = cyanodithioimidocarbonate) and their I2-doped products have been prepared and characterized by microanalysis, magnetic and solution as well as solid phase conductivity measurements, IR, Raman, electronic, 1H and 13C NMR and ESR spectroscopic techniques. ESR silent diamagnetic compounds [PhHg]2[Cu(cdc)2], [Me2Sn][Cu(cdc)2], [n-Bu2Sn][Cu(cdc)2], [n-Bu3Sn]2[Cu(cdc)2] and [Ph3Sn]2[Cu(cdc)2] are strongly antiferromagnetically coupled. [PhHg]2[Ni(cdc)2] is weakly paramagnetic because of the weak axial interactions of sulfur atoms of the ligand cdc2− with some of the Ni(II) centers. Sharp 1H NMR signals suggest that [PhHg]2[Cu(cdc)2], [n-Bu2Sn][Cu(cdc)2], [n-Bu3Sn]2[Cu(cdc)2] and [Ph3Sn]2[Cu(cdc)2] remained diamagnetic in solution as well. Majority of the complexes exhibited σrt in the range of 10−11 to 10−10 S cm−1 while the I2-doped products show enhanced conductivity in the 10−10 to 10−6 S cm−1 range and exhibit semiconducting behaviour.