The synthesis of the organometallic d(2) [Cp*W(dmit)(2)](1-) complex (where Cp* is pentamethylcyclopentadienyl and dmit is 1,3-dithiole-2-thione-4,5-dithiolate), and its oxidation to the paramagnetic d(1) [Cp*W(dmit)(2)]* Species, is described and their X-ray crystal structures given. Geometrical evolutions upon oxidation, characterized by a variable folding of the WS2C2 metallacycles along the S-S hinge, are rationalized by density functional theory (DFT) calculations and by comparison with the molybdenum analogs; as is also the evolution in the UV-vis-NIR absorption spectra. In solution, only the d(1) complexes exhibit positive optical density variations in transitory nanosecond spectroscopy after 10 ns laser pulses. A weak optical limiting effect was observed on these d(1) species, stronger in the W than in the Mo complex. In the solid state. the interacting, paramagnetic [Cp*W(dmit)(2)]* species (theta(Curie-Weiss) = -20 K) orders antiferromagnetically below T-Neel = 4.5 K with a spin-flop field, B-SF(W) Of 8000 G. Compared with the molybdenum analog, the weaker theta(Curie-Weiss)(W) and T-Neel[(W) values, and larger B-SF(W) values reflect weaker intermolecular interactions due to a decreased spin density on the dithiolene ligands and stronger spin-orbit coupling with the W atom, as confirmed by DFT calculations on the d(2) and d(1) Mo and W complexes.