Ion-promoted, automorphogenic, and stoichiometric self-assembly of a hexameric, Ru-based macrocycle and a dodecacarboxylate-terminated dendrimer produced a stable nanofiber. For comparison, the structurally related larger 3rd generation dendrimer. ideally terminated with 108 carboxylic acids, was reacted with (1(12+))(PF6-)(12) to afford a neutral, sphere-like motif. These polyanionic dense-packed counterions lead to ion-pair superstructures in which the randomness of single-charged counterions has been eliminated.