Ligand-Induced Assembly of Coordination Chains and Columns Containing High-Nuclearity Silver(I) Ethynide Cluster Units

The multinuclear metal–ligand supramolecular synthon RC6H4CC⊃Agn (R = Me, F; n = 3–5) has been employed to construct the two high-nuclearity silver ethynide cluster compounds [(NO3)2@Ag26(o-MeC6H4CC)16]­(NO3)8·5H2O (1) and [NO3@Ag15(o-FC6H4CC)10]­(NO3)4 (2), which bear the same nitrate central core. The synthesis of [CrO4@Ag18(iPrCC)12]­(ClO4)4 (3) and [ClO4@Ag18(iPrCC)12]­(ClO4)5 (4) demonstrated the effect of variation of central anionic core size and charge on the construction of multidimensional organosilver­(I) networks. The bulkiness of the peripheral ligands and the orientation of substituents with respect to the ethynide group proved to be dominant factors that direct the formation of high-nuclearity clusters and the assembly of coordination networks. To our knowledge, 1 and 2 are the first examples using the nitrate anion for templated cluster synthesis.