The combination of bisamidinium dicationic tectons [XX–2H+] (XX = 2–4) bearing four alkyl chains of variable lengths with linear [M(CN)2]− (M = Ag or Au) anions leads to the formation of luminescent crystalline materials. The recognition mode, the connectivity patterns between cationic and anionic tectons leading to the formation of either 1- or 2-D networks as well as the packing of the latter are presented and discussed.