Overlooked Effects of La-4f Orbitals in Endohedral Metallofullerenes

For endohedral metallofullerenes (EMFs), a central issue is how to correctly describe the intracluster and metal–cage interactions, which are critical for understanding their structures, stabilities, and various properties. In this work, density functional theory calculations were carried out for 13 La-based EMFs covering all four reported types and a rather wide cage size range (C₃₂–C₁₀₄). The results reveal that the usually core-like lanthanide 4f subshell may play a critical role in the structural characteristics, energetic stabilities, frontier orbital energy levels, metal charges, and chemical reactivities of these endofullerenes. Regardless of the encapsulated forms, the La-4f contributions to the chemical bonding and structural stability increase with the reduced cage sizes because of the gradually enhanced cage confinement. The combination of metal-to-nonmetal charge transfer and compression of the cage cavity exposes and effectively activates the otherwise chemically inert 4f orbitals. By disclosing the important role of long-neglected metal orbitals inside fullerenes, the current work not only deepens our understanding of EMFs, but also provides new insights into the chemical bondings in general confined spaces at the subnanometer scale.