Rapidly expanding research in nanotechnology has led to exciting progress in a versatile array of applications from medical diagnostics to photocatalytic fuel cells. Such success is due to the ability of researchers to manipulate the desired properties of nanomaterials by controlling their size, shape, and composition. Among the most thriving areas of nanoparticle research has been the synthesis and characterization of stable metallic nanoclusters capped by thiolate ligands. Our group has extended this research to study copper, silver, and gold clusters with remarkable stability and energetics, which was achieved by using dithiolates as the ligand stabilizers. In addition to the enhanced stability offered by the chelate effect, the use of dithiolate ligands instead of monothiolates is proposed to provide an alternate interfacial bond structure that is shown to strongly influence energetic properties of nanoclusters, with strong evidence of metal-ligand charge transfer. Energetic properties were characterized by spectroscopic and electrochemical methods.