We present the formation of the largest titanium–oxo cluster, [Ti₄₂(μ₃-O)₆₀(OiPr)₄₂(OH)₁₂)]^6-, with the first fullerene-like Ti–O shell structure. The {Ti₄₂O₆₀} core of this compound exemplifies the same icosahedral (Ih) symmetry as C₆₀, the highest possible symmetry for molecules. According to the coordination environments, the Ti centers in this cluster can be arranged into a Platonic {Ti₁₂} icosahedron and an Archimedean {Ti₃₀} icosidodecahedron. The solution stability of this cluster was confirmed by electrospray ionization mass spectrometry. The spherical body of the {Ti₄₂O₆₀} core has an inside diameter of 1.05 nm and an outside diameter of 1.53 nm, which could be directly visualized by high-resolution transmission electron microscopy. Our results demonstrate that titanium oxide can also form fullerene-like shell structures.

http://pubs.acs.org/doi/abs/10.1021/jacs.6b00613