High-Nuclearity Heterometallic tert-Butylethynide Clusters Assembled with tert-Butylphosphonate.

tert-Butylphosphonic acid and lanthanide precursors were employed to construct two high-nuclearity hybrid silver(I)-ytterbium(III) phosphonate clusters: compound 1 consists of a Ag16 ethynide cluster fused with a trinuclear hydroxoytterbium phosphonate cluster, whereas compound 2 is composed of two Ag16 ethynide clusters bridged by a hexanuclear oxo/hydroxoytterbium phosphonate cluster. Using transition-metal-substituted lacunary polyoxotungstates in place of the lanthanide reactant, new phosphonate-functionalized silver(I)-copper(II) ethynide clusters [Ag34 Cu6 (3) and Ag37 Cu6 (4)] and silver(I) ethynide clusters [Ag51 (5) and Ag72 (6)] were obtained. The structures of complexes 3-6 feature core-shell arrangements, in which silver(I)-copper(II) or silver(I) ethynide cluster shells stabilized by peripheral phosphonate ligands enclose different kinds of tungstate core templates.