Reaction of the ligands 1,2-C6H4{NHC(O)-4-C5H4N}2 (1) and 1,2-C6H4{NHC(O)-3-C5H4N}2 (2) with silver(I) salts AgX, X = CF3CO2, NO3, CF3SO3, and PF6, gave the corresponding complexes [(AgX)(μ-LL)]n, 3a−4d (3a−3d: LL = 1; 4a−4d: LL = 2; a, X = CF3CO2; b, X = NO3; c, X = CF3SO3; d, X = PF6). The complexes probably exist in solution primarily as the disilver(I) macrocyclic complexes [{AgX(μ-LL)}2] or [Ag2(μ-LL)2]X2, but in the solid state they may exist as either macrocycles or polymers [{AgX(μ-LL)}n] or [Agn(μ-LL)n]Xn. The silver(I) centers have distorted tetrahedral stereochemistry when X = CF3CO2 or NO3 but roughly linear stereochemistry when X = CF3SO3 or PF6, and it is argued that the hierarchy of control in the self-assembly process is by the bonds Ag−N > Ag−O > NH···OC when X = CF3CO2 or NO3, but Ag−N > NH···OC > Ag···O or Ag···F when X = CF3SO3 or PF6. In complexes 3a and 3b, macrocyclic complexes are connected to form polymers or sheets, respectively, through bridging anions, whereas polymers of 4a ...