Endohedral metallofullerenes based on spherical I(h)-C(80) cage: molecular structures and paramagnetic properties.

Fullerenes are carbon cages assembled from fused hexagons andpentagons that have closed networks and conjugated π systems. The curve of the fullerene structure requires that the constituent carbon atoms take on a pyramidal shape and produces extra strain energy. However, the highly symmetrical geometry of the fullerene decreases the surface tension in these structures, so highly symmetrical fullerenes are usually very stable. For example, C60 with icosahedral symmetry (Ih) is the most stable fullerene molecule. However, another highly symmetrical fullerene, Ih-C80, is extremely unstable. The reason for this difference is the open-shell electronic structure of Ih-C80, which has a 4-fold degenerate HOMO occupied by only two electrons. Predictably, once the degenerate HOMO of Ih-C80 accepts six more electrons, it forms a closed-shell electronic structure similar to Ih-C60 and with comparable stability. Because the hollow structure of fullerenes can encapsulate metal atoms and those internal metals can transfer electrons to the fullerene cage, the encapsulation of metal clusters may provide an ideal technique for the stabilization of the Ih-C80 fullerenes. In this Account, we focus on the molecular structures and paramagnetic properties of spherical Ih-C80 endohedral fullerenes encaging a variety of metal moieties, such as metal atoms (Mn), metal nitride (M3N), metal carbide (MnC2), metal carbonitride (M3CN), and metal oxides (M4Om). We introduce several types of endohedral metallofullerenes such as Sc4C2@Ih-C80, which exhibits a Russian-doll-like structure, and Sc3CN@Ih-C80, which encapsulates a planar metal carbonitride cluster. In addition, we emphasize the paramagnetic properties of Ih-C80-based metallofullerenes, such as Sc3C2@Ih-C80, Y2@C79N, and M3N@Ih-C80, to show how those spin-active species can present a controllable paramagnetism. This Account highlights an inspiring molecular world within the spherical Ih-C80 cages of various metallofullerenes.