The synthesis of a new class of supermolecules with cofacially-oriented, planar subunits employs the [Mo2O5](2+) bridge unit and catechol-functionalized, metalated macrocyclic [M(TAD-(OH)2)] and SALPHEN [M(EtO(2)SALPHEN-(OH)(2))] ligands. Of the reported (Bu(4)N)(2)[Mo2O5[Ni(TAD-(O)(2))](2)] and (Bu(4)N)(2)[Mo2O5[M(EtO(2)-SALPHEN-(O)(2))](2)] (M = H-2, Cu, Ni) complexes, the structurally characterized (Bu(4)N)(2)[Mo2O5[Ni(TAD-(O)(2))](2)] shows the two Ni atoms separated by 3.938 Angstrom. The structure of (Bu(4)N)(2)[Mo2O5[Cu(EtO(2)SALPHEN-(O)2)](2)] shows two Cu atoms separated by 4.110 Angstrom.