It is shown that multiple ionization energies of metal-chalcogenide clusters can be substantially reduced by adding ligands that form charge transfer complexes. We demonstrate this intriguing phenomenon by considering metal-chalcogenide clusters including cases where a cluster has a filled electronic shell with a large gap between the occupied and unoccupied states reminiscent of stable species. The studies include a Co6Se8 core ligated with tri-ethylphosphine (PEt3) ligands forming a stable Co6Se8(PEt3)(6) species. All of the ligated clusters have a first ionization energy in the range for alkali atoms and multiple ionization energies that are considerably lower than those for the non-ligated clusters. The change in electronic behavior upon ligation can be associated with a shift in the electronic spectrum via a crystal field like effect due to attaching ligands that form charge transfer complexes. We also show that metal-chalcogenide species can be programmed by proper ligand replacement to promote dimerization by first forming the Co6Se8(PEt3)(n)(CO)(6-n) (n = 0-6) clusters where the CO ligands could be replaced by diisocyanide (CNC6H4NC) ligands. The diisocyanide ligand acts as a rigid linker between the metallic cores, enabling the formation of a Co6Se8(PEt3)(5)(CNC6H4NC)-Co6Se8(PEt3)(5) superatomic molecule (SM), and we examine the electronic and magnetic properties of the recently synthesized SM via studies on an analogous SM with smaller ligands.