The potential of [L2Pd(2,2′-bpz-N1,N1′)]2+ [L2 = en (1), L = H2O (4a), 2,2′-bpz = 2,2′-bipyrazine] for use as an angular element in the generation of self-organized systems of variable molecular architecture has been studied. Ag+ forms an infinite loop 3 with 1, in which the metal ions function as cross-linking agents between the organic entities 2,2′-bpz. Complex 4a, on the other hand, self-assembles as a bis(μ-OH) dinuclear species 4b, and in the presence of 4,4′-bipyridine (4,4′-bpy) as a molecular square 6 with the heteroaromatic 4,4′-bpy ligands representing the cross-linking entities.