A comprehensive study of the electronic structure of nanoscale molecular oxide capsules of the type [{M^VI (M^VI )₅ O₂₁}₁₂ {M’^V₂ O₂ (μ-X)(μ-Y)(L^n- )}₃₀ ]^(12+n)- is presented, where M,M’=Mo,W, and the bridging ligands X,Y=O,S, carried out by means of density functional theory. Discussion of the electronic structure of these derivatives is focused on the thermodynamic stability of each of the structures, the one having the highest HOMO-LUMO gap being M=W, M’=Mo, X=Y=S. For the most well-known structure M=M’=Mo, X=Y=O, [Mo₁₃₂ O₃₇₂ ]^12- , the chemical bonding of several ligands to the {Mo^V₂ O₂ (μ-O)₂ } linker moiety produces negligible effects on its stability, which is evidence of a strong ionic component in these bonds. The existence of a hitherto unknown species, namely W₁₃₂ with both bridging alternatives, is discussed and put into context.