The interesting case of long intramolecular d 10-d 10 contacts has been studied through [Ag 4L 2] 2+ and [Au 4L 2] 2+ (L = 3,5-bis((N-methylimidazolyl) methyl)pyrazole) systems, showing interesting features gained by analysis of the electronic structure and the overall shielding tensor in the molecular domain, in terms of its components. The long intramolecular closed-shell separations are attributed to the population of the bonding, nonbonding, and antibonding combinations of the ns atomic shells in the [M 4] 4+ core, contrasting with that observed in systems with shorter d 10-d 10 distances. This point allows to concludeb that separations shorter then the sum of the van der Waals radii (3.4 Å for Ag-Ag, and 3.2 Å for Au-Au) of the nucleus involved requires a net bonding population between ns and np atomic shells of the d 10 closed-shell centers. Moreover, [Au 4L 2] 2+ exhibits an increased covalency observed for the enhanced charge-donation due to the stabilization of the ns and destabilization of the (n - 1)d driven by the relativistic effects. The magnetic response denotes a slight interaction between the closed-shell centers at distances in the range of their sum of van der Waals radii because the observed remote effect (or anisotropic effect) caused by each d 10 nucleus does not influence considerably the neighbor center. The analysis of δ in terms of its components allows to conclude that the [Au 4L 2] 2+ system exhibits an increased magnetic response due to the increase in the number of the inner-electrons in comparison to [Ag 4L 2] 2+. © 2012 American Chemical Society.