Self‐Assembly Engineering of Fullerene‐Like Polyhedra: V₆₀, V₆₆, V₇₂ From {MV₅} Pentagonal Second Building Block

The synthesis of hollow fullerene-like cages has always been an attractive goal for researchers. Nevertheless, such molecular design blueprints are often hampered by the unmet customization of assembly strategy and suitable five-membered ring molecular tiles for building spheres. Herein, a novel spherical molecular cage V₆₀-MOP is successfully built by connecting 12 homo-metallic pentagonal {V₅S} tiles with benzene-1,3,5-tricarboxylate (BTC) ligands through coordination-driven self-assembly and exhibits a similar geometry to the C₆₀ molecule. As far as is known, this {V₅S} cluster with the shape of a hollow pentagram is entirely new and is first discovered in metal-organic polyhetra (MOPs). The other two pentagonal motifs are also customized by inserting [VO₅] or [MoO₅] in the center of {V₅S} through in situ modification, which also led to another isomorphic V₇₂-MOP and V₆₀Mo₁₂-MOP fullerene-like cages. The three spherical cages reported above all exhibit regular icosahedral symmetry. Notably, a fascinating structure V₆₆-MOP is constructed from two different pentagonal motifs {V₅S} and {VV₅S}, with reduced symmetry, although the molecule remains a sphere in appearance, which is rare in fullerene-shaped structures. In addition, the series of fullerene-like V-MOPs are active in the oxidation of sulfides to produce sulfoxides or sulfones with high conversion.