The synthesis, spectral and thermal properties of dicyanoargentates, namely Cu(tn)(2)Ag-2(CN)(4) (I) (tn = 1,3-diaminopropane), Cu8-xAgx(tn)(3) (CN)(10) x = 0.25 (II), Cu(pn)(2)Ag-2(CN)(4) (III) (pn = 1,2-diaminopropane) and Cu-2(dabn)(2)(NH3)Ag-4(CN)(8).2H(2)O (IV) (dabn = 1,4-diaminobutane) are reported. All complexes were isolated from reaction mixtures containing K[Ag(CN)(2)], CuSO4 and N-donor ligands (tn, pn and dabn, respectively). Infrared spectra confirm the presence of characteristi c functional groups and are consistent with the known structures of complexes (I), (III) and (IV). Thermal decompositions of complexes (I)-(IV) begin by endothermic liberation of ligand molecules followed by strong exothermic redox decomposition of the cyano groups. Comparison of the initial decomposition temperatures of complexes (I)-(IV) yields the following order of the thermal stability (IV) < (I) < (III) < (II). (C) 2004 Elsevier B.V. All rights reserved.