Fullerene‐like Niobovanadate Cage Built from {(Nb)V5} Pentagon

The striking aesthetic appeal of fullerene-like clusters has captured the interest of researchers. Nevertheless, the assembly of fullerene-like polyoxovadanadate (POV) cages remains a significant challenge due to the scarcity of suitable pentagonal motif. Herein, we have successfully synthesized the first fullerene-like all-inorganic POV cage, {(V₂ O)V₃₀ Nb₁₂ O₁₀₂ (H₂ O)₁₂ } (V₃₀ Nb₁₂ ), by introducing Nb into the POVs. V₃₀ Nb₁₂ is assembled by 12 heterometallic {(Nb)V₅ } pentagons through sharing V centers with I_h symmetry, reminiscent of C₆₀ . To our knowledge, the fullerene-like V₃₀ Nb₁₂ not only represents the highest-nuclearity POV cage but also stands as the first niobovanadate cluster. Notably, V₃₀ Nb₁₂ exhibits excellent solution stability, as confirmed by ESI-MS, FT-IR and UV/Vis spectra. As there is no protection organic ligand on its outer surface, V₃₀ Nb₁₂ can be further modified with Cu-complexes to form a fullerene-like cluster based zigzag chain (Cu-V₃₀ Nb₁₂ ).