Anderson-like alkoxo-polyoxovanadate clusters serving as unprecedented second building units to construct metal-organic polyhedra.

Unprecedented Anderson-like alkoxo-polyoxovanadate [V6O6(OCH3)9(μ6-SO4)(COO)3](2-) polyanions can serve as 3-connected second building units (SBUs) that assemble with dicarboxylate or tricarboxylate ligands to form a new family of metal organic tetrahedrons of V4E6 and V4F4 type (V = vertex, E = edge, and F = face). To our knowledge, this alkoxo-polyoxovanadate-based SBU is the first ever reported.