Five new Ag(I) complexes of the formulae {[Ag-2(L-1)(2)(NDS)](3)H2O}(n) (1), {[Ag-2(L-2)(2)(NDS)]center dot 2H2O}(n) (2), {[Ag-3(L-2)(2)(IQS)(2)]center dot(NO3)center dot 4H(2)O center dot 2MeOH}(n) (3), {[Ag-2(L-3)(2)(NDS)]center dot 4H(2)O}(n) (4), and {[Ag-2(L-3)(2)(IQS)]center dot(NO3)center dot H2O}(n) (5) (L-1 = 2,5-bis-pyridine-3-ylmethylene-cyclopentanone, L-2 = 2,5-bis-pyridine-3-ylmethylene-cyclohexanone, L-3 = 2,5-bis-pyridine-4-ylmethylene-cyclopentanone, NDS = naphthalene disulfonate, and IQS = isoquinoline-5-sulfonate) have been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complexes 13 were found to have sulfonate supported Ag center dot center dot center dot Ag interaction, and the sulfonate ions act as linkers to form higher dimensional networks (ladder, two- and three-dimensional networks). The complexes 4 and 5, which contain 4-pyridyl substitution, do not form such Ag center dot center dot center dot Ag interactions, indicating a clear tendency of 3-pyridyl derivatives to promote such interactions over 4-pyridyl derivatives. This observation was also evidenced by the analysis of Ag(I) complexes in Cambridge Structural Database. Further, complexes 15 were found to exhibit solid-state photoluminescence in the green region at room temperature.