Doping potassium ions in silver cyanide complexes leads to two heterometallic silver–potassium cyanide complexes, namely, [Me4N]2[KAg3(CN)6] (1) with a typical NaCl-type framework containing distinct ligand-unsupported argentophilic interactions, and [Ag3(H2O)3][K(CN)2]3 (2) with an unprecedented 3-D (4,4,6,6)-connected framework formed by unique [Ag3(H2O)3] clusters connecting concave–convex 2∞[K(CN)2] layers. The two complexes exhibit green luminescence, and the relationships between their structures and photoluminescence, as well as the regulating effect on the luminescence by doping of potassium ions are well investigated via density functional theory analysis.
