A systematic study has been carried out on a range of metal complexes of the type (cation)(n)[M(dmit)(2)] (cation = NH(y)R(4-y); y = 1 or 2; n = x, 1, 2; R = ethyl, propyl or butyl, or cation = organic radical cations containing one or two TTF moieties; M = Ni or Pd and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato). The synthesis of these complexes, the crystal structure of (NHBu(3))(2)[Ni(dmit)(2)] and neutral [Ni(dmit)(2)], their solution redox behaviour and the solid state conductivities of the non-integer oxidation state compounds obtained by electrocrystallization techniques are presented. Synthesis, structure and properties of new compounds of the family of (BETS)(2)(anion) compounds with (CuxCly)(n-) and[(FeCl4)(1-x)(GaCl4)(x)](-) anions are described.