Halide-ion-templated Ag8Cu6 rhombic dodecahedrons: synthesis, structure and reactivity of [Ag8Cu6(CCtBu)12X]BF4 (X = Cl, Br)

Halide-templated tert-butylethynide Ag14 complexes undergo reversible exchange with copper(I) to afford a series of mixed Ag14-nCun (n = 1-6) species. Up to six silver atoms in the cluster can be replaced with copper(I) to give a core structure featuring a Ag8Cu6 rhombic dodecahedron. These clusters are useful models for investigating the chemical reactivity and photoluminescence of heterometallic d(10)-d(10) systems.