Assembly of high-symmetry silver(i) alkyl-1,3-diynyl cluster complexes via core transformation.

New tetranuclear supramolecular precursors [(R-C C-C C) Ag (PPh3)](4) (R = iPr and chx) are employed to construct three polynuclear silver(I) alkyl-1,3-diynyl cluster complexes (1-3) that bear the same novel trigonal bipyramidal Ag-5 core consolidated by silver-ethynide and argentophilic interactions. The present results strongly suggest that the assembly of high-symmetry mediumnuclearity clusters 1-3 is initiated by the accretion of additional Ag(I) ions by the Ag-4 template of the precursors through argentophilic (< 3.4 angstrom)interaction, and demonstrate that core transformation is an effective synthetic route to high-symmetry metal clusters.