(PhSe) 2Hg reacts initially with HgX 2 (X = Cl, I) and further with triphenylphosphine/DMF to give (PhSe) 7Hg 4ClPy n ( 1) and (PhSe) 7Hg 4I(DMF) n ( 2), polymeric assemblies of (μ-Se)Hg clusters obtained through coordinating intermediary ligands. Each single adamantoid molecule of 1 and 2 presents the Hg II ions with a distorted tetrahedral configuration linked through asymmetric μ-(Ph)Se − bridges. (PhSe) 7Hg 4ClPy n and (PhSe) 7Hg 4I(DMF) n are further examples of extended one-dimensional chains of closed anisotropic ME (E = S, Se, Te) systems. In these reactions the features of the intermediary ligands should determine the template which leads to single adamantane moieties or to fused ones. (PhSe) 2Hg reacts initially with HgX 2 (X = Cl, I) and further with triphenylphosphine/DMF to give (PhSe) 7Hg 4ClPy n ( 1) and (PhSe) 7Hg 4I(DMF) n ( 2), polymeric assemblies of (μ-Se)Hg clusters obtained through coordinating intermediary ligands. Each single adamantoid molecule of 1 and 2 presents the Hg II ions with a distorted tetrahedral configuration linked through asymmetric μ-(Ph)Se − bridges. (PhSe) 7Hg 4ClPy n and (PhSe) 7Hg 4I(DMF) n are further examples of extended one-dimensional chains of closed anisotropic ME (E = S, Se, Te) systems. In these reactions the features of the intermediary ligands should determine the template which leads to single adamantane moieties or to fused ones.