The Self-Assembly of [{Ag3(C≡CtBu)2}n]n+ Building Units into a Template-Free Cuboctahedron and Anion-Encapsulating Silver Cages.

We describe the controlled synthesis of silver acetylide clusters based on a simple polymeric [Ag3L2]+ (L = -C≡CtBu) building block. A linear one-dimensional polymeric structure shows alternating pyramidal motifs and is the basic repeating unit forming discrete molecular cages (pentamers [X⊂Ag15L10]4+ and hexamers [PF6⊂Ag18L12]5+) obtained by incorporating suitable templates. These motifs and a rare template-free cuboctahedral [Ag12L8]4+ cluster (tetramer) were crystallographically characterized.