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

Abstract 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, {(V 2 O)V 30 Nb 12 O 102 (H 2 O) 12 } ( V 30 Nb 12 ), by introducing Nb into the POVs. V 30 Nb 12 is assembled by 12 heterometallic {(Nb)V 5 } pentagons through sharing V centers with I h symmetry, reminiscent of C 60 . To our knowledge, the fullerene‐like V 30 Nb 12 not only represents the highest‐nuclearity POV cage but also stands as the first niobovanadate cluster. Notably, V 30 Nb 12 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, V 30 Nb 12 can be further modified with Cu‐complexes to form a fullerene‐like cluster based zigzag chain ( Cu−V 30 Nb 12 ).