A series of new heterometallic coordination polymers has been prepared from the reaction of metal-ligand cations and KAg(CN)(2) units, Many of these contain silver-silver (argentophilic) interactions, analogous to gold-gold interactions, which serve to increase supramolecular structural dimensionality. Compared to [Au(CN)(2)](-) analogues, these polymers display new trends specific to [Ag(CN)(2)](-), including the formation of [Ag-2(CN)(3)](-) and the presence of Ag...N interactions. [Cu(en)(2)][Ag-2(CN)(3)][Ag(CN)(2)] (1, en = ethylenediamine) forms 1-D chains of alternating [Ag(CN)(2)](-) and [Ag-2(CN)(3)](-) units via argentophilic interactions of 3.102(1) Angstrom. These chains are connected into a 2-D array by strong cyano(N)-Ag interactions of 2.572(3) Angstrom, [Cu(dien)Ag(CN)(2)](2)[Ag-2(CN)(3)][Ag(CN)(2)] (2, dien = diethylenetriamine) forms a 1-D chain of alternating [Cu(dien)](2+) and [Ag(CN)(2)](-) ions with the Cu(II) atoms connected in an apical/equatorial fashion. These chains are cross-linked by [Ag-2(CN)(3)](-) units via argentophilic interactions of 3.1718(8) Angstrom and held weakly in a 3-D array by argentophilic interactions of 3.2889(5) Angstrom between the [Ag(CN)(2)](-) in the 2-D array and the remaining free [Ag(CN)(2)](-). [Ni(en)][Ni(CN)(4)].2.5H(2)O (4) was identified as a byproduct in the reaction to prepare the previously reported [Ni(en)(2)Ag-2(CN)(3)][Ag(CN)(2)] (3), In [NI(tren)Ag(CN)(2)][Ag(CN)(2)] (5, tren = tris(2-aminoethyl)amine), [NI(tren)] 2, cations are linked in a cis fashion by [Ag(CN)(2)](-) anions to form a 1-D chain similar to the [Au(CN)(2)](-) analogue, [Cu(en)Cu(CN)(2)Ag(CN)(2)] (6) is a trimetallic polymer consisting of interpenetrating (6,3) nets stabilized by d(10)-d(10) interactions between Cu(I)-Ag(I) (3,1000(4) Angstrom). Weak antiferromagnetic coupling has been observed in 2, and a slightly stronger exchange has been observed in 6. The Ni(II) complexes, 4 and 5, display weak antiferromagnetic interactions as indicated by their relatively larger D values compared to that of 3. Magnetic measurements on isostructural [Ni(tren)M(CN)(2)][M(CN)(2)] (M = Ag, Au) show that Ag(I) is a more efficient mediator of magnetic exchange as compared to Au(I). The formation of [Ni(CN)(4)](2-), [Ag-2(CN)(3)](-), and [Cu(CN)(2)](-) are all attributed to secondary reactions of the dissociation products of the labile KAg(CN)(2).