The syntheses, crystal structures as well as the spectral characterizations including IR, Raman, UV-Vis and ⁹⁵Mo NMR of nine trinuclear molybdenum-sulfur cluster compounds were systematically reported. It is shown from the results of the crystal structure analysis that their cluster cores are different. [Mo₃(μ₃-S)(μ-S)₃] core is for 1 and 6; [Mo₃(μ₃-S)(μ-O)(μ-S)₂] core for 2 and 3, [Mo₃(μ₃-O)(μ-S)₃] core for 4, 5, 7, 8 and [Mo₃(μ₃-S)(μ-S₂)₃] core for 9. In this paper, the different packing structures for these compounds along with a variety of cluster cores and the peripheral bridging ligands or loosely coordinated terminal ligands were described. The electronic structures of the first three cluster cores were also discussed. Moreover, a rational interpretation for some important spectral results has been made based on their stereo and electronic structures. Finally, the temperature dependence of the electric conductivity of 4 has been measured, indicating that this compound exhibits the electroconductivity of semiconductor.

Key words: trinuclear molybdenum-sulfur cluster, substituted ligand with aryl group, synthesis, crystal structure, spectral characterization, electronic structure, conductivity