Sc 2 @ C 66 . Spherical Aromaticity in a Markedly Ellipsoidal Endohedral Metallic Fullerene

ABSTRACT Incorporation of metallic atoms into fullerenes leads to the characterization of nonclassical cage landscapes, highlighting the markedly ellipsoidal Sc 2 @C 2v (4059)‐C 66 structure. In this work, we set out to explore Sc 2 @C 2v (4059)‐C 66 and its Stone‐Wales transformation isomer (Sc 2 @ C 2v ‐(3441)‐C 66 ) in terms of the resulting characteristics provided by the donation of six electrons from the metallic atoms into the π‐electron C 66 kernel in terms of induced magnetic field characteristics. The Sc 2 @C 66 species shows a long/short axis ratio surpassing that of C 70 , featuring two sets of three consecutively fused pentagons at the poles. From the resulting electron transfer from two encapsulated Sc atoms to the C 66 cage, resulting in a 72 π‐electron system that fulfills Hirsch's 2( N + 1) 2 spherical aromaticity rule ( N = 5). Our results support the formation of a spherical aromatic endohedral metallic fullerene (EMF) despite the elongated shape, which shows the absence of a direct Sc‐Sc bond. The Stone‐Wales transformation connecting both isomers modulates their local electronic and magnetic properties, having a lesser impact on the global aromatic properties. These findings highlight the persistence of spherical aromatic characteristics and adaptability in relation to structural rearrangements within an ellipsoidal EMF, as a suitable building block for applications in supramolecular chemistry and related fields.