Self‐Assembly Engineering of Fullerene‐Like Polyhedra: V 60 , V 66 , V 72 From {MV 5 } Pentagonal Second Building Block

Abstract 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 V 60 ‐MOP is successfully built by connecting 12 homo‐metallic pentagonal {V 5 S} tiles with benzene‐1,3,5‐tricarboxylate (BTC) ligands through coordination‐driven self‐assembly and exhibits a similar geometry to the C 60 molecule. As far as is known, this {V 5 S} 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 [VO 5 ] or [MoO 5 ] in the center of {V 5 S} through in situ modification, which also led to another isomorphic V 72 ‐MOP and V 60 Mo 12 ‐MOP fullerene‐like cages. The three spherical cages reported above all exhibit regular icosahedral symmetry. Notably, a fascinating structure V 66 ‐MOP is constructed from two different pentagonal motifs {V 5 S} and {VV 5 S}, 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.