Reaction of the ditopic semirigid ligand 1,2-bis(imidazolylmethyl)benzene (1,2-bImb) or the flexible ligand 1,4-bis(2-benzimidazolyl)butane (C4BIm) with AgX (X = ClO4-, BF4-, CF3CO2-) afforded five new complexes, namely, [Ag2(1,2-bImb)2](ClO4)2 (1), [Ag2(1,2-bImb)2](BF4)2 (2), [Ag2(1,2-bImb)2](CF3CO2)2.2CH3OH (3.2CH3OH), [Ag2(C4BIm)2](ClO4)2.2DMF (4.2DMF), and [Ag2(C4BIm)2](CF3CO2)2.2H2O (5.2H2O), all of which contain a centrosymmetric, rectangular-shaped cationic disilver(I) metallacycle [Ag2(L)2]2+. In 1-3, a pair of 1,2-bImb ligands takes on the syn conformation to connect two Ag(I) ions to give a compressed rectangle with a transannular Ag...Ag separation of 3.27-3.36 angstroms, whereas in 4 and 5, the pair of planar C4BIm ligands acts in the cis conformation to connect two Ag(I) ions to yield a normal rectangle with a transannular Ag...Ag separation of 7.67-7.91 angstroms. The anions form Ag...O or Ag...F weak interactions in 1-3 and O-H...O or N-H...O hydrogen bonds in 4 and 5 in crystal packing but exhibit no significant influence on the formation of the disilver(I) macrocycles. The solution structure and dynamic behavior of the complexes studied by electrospray ionization mass spectrometry, 1H NMR, and variable-temperature NMR indicated that the dynamic equilibrium between the [Ag2(L)2]2+ cation and the open-ring oligomers or other potential species occurs via solvent-assisted dissociative exchange. The metal-ligand exchange barrier was estimated to be 54.5 kJ mol(-1).