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

New tetranuclear supramolecular precursors [(R-CC-CC)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 Ag₅ core consolidated by silver-ethynide and argentophilic interactions. The present results strongly suggest that the assembly of high-symmetry medium-nuclearity clusters 1-3 is initiated by the accretion of additional Ag(i) ions by the Ag₄ template of the precursors through argentophilic (<3.4 Å) interaction, and demonstrate that core transformation is an effective synthetic route to high-symmetry metal clusters.