The magnetic exchange coupling constants between two Mn(II) centers fora set of five inverse crown structures have been investigated by means of a methodology based oil broken-symmetry unrestricted density functional theory. These novel and highly unstable compounds present superexchange interactions between two Mn centers, each one with S = 5/2 through anionic "guests" Such as oxygen, benzene, or hydrides or through the cationic ring formed by amide ligands, and alkali metals (Na, Li). Magnetic exchange Couplings calculated at B3LYP/6-31G(d,p) level yield strong antiferromagnetic couplings for compounds linked via all oxygen atom or hydride and very small antiferromagnetic Couplings for those linked via a benzene molecule, deprotonated in either 1,4- or 1,3- positions. Analysis of the magnetic orbitals and spin polarization maps provide ail Understanding of the exchange mechanism between the Mn centers. The dependence of J with respect to 10 different density functional theory potentials employed and the basis set has been analyzed.