Biological systems employ multimetallic assemblies to achieve a range of functions. Here we demonstrate the preparation of metal-organic cages that contain either homobimetallic or heterobimetallic vertices. These vertices are constructed using 2-formyl-6-diphenylphosphinopyridine, which forms ligands that readily bridge between a pair of metal centers, thus enforcing the formation of bimetallic coordination motifs. Two pseudo-octahedral homometallic ML cages (M = Cu or Ag) were prepared, with a head-to-head configuration of their vertices confirmed by X-ray crystallography and multinuclear NMR for Ag. The phosphino-pyridine subcomponent also enabled the formation of a class of octanuclear CdCuL tetrahedral cages, representing an initial example of self-assembled cages containing well-defined heterobimetallic vertices.
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