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.