The effect of the anion on the assembly reactions of an O2S2-macrocycle L with AgX (X = NO3−, BF4−, CF3SO3− or CF3CO2−) has been demonstrated to yield four supramolecular complexes (1–4) with different topologies: the exocyclic 2-D rectangular-grid coordination polymer [Ag(L)NO3]n (1), the endo-/exocyclic discrete cyclic tetramer [Ag4(L)4(BF4)2(CH3OH)2](BF4)2 (2), and the exocyclic 2-D coordination polymers [Ag(L)X]n (3; X = CF3SO3 and 4; X = CF3CO2).
