Aromaticity Survival in Hydrofullerenes: The Case of C₆₆ H₄ with Its π-Aromatic Circuits

The isolated-pentagon rule (IPR) is a determining structural feature that accounts for hollow fullerene stabilization and properties related to C_n (n≥60) cages. The recent characterization of an unprecedented non-IPR hydrofullerene, C_2v C₆₆ H₄ , bearing two heptagons with adjacent fused-pentagon motifs, largely dismisses this feature. Herein, employing DFT calculations, the ¹³ C NMR spectroscopy and aromatic behavior of C_2v C₆₆ H₄ are explored. The results show the presence of three π-aromatic circuits at the bottom boat section of C₆₆ H₄ , indicating the unique features of this hydrofullerene in comparison to those of pristine C₆₀ . In addition, under specific orientations of the external field, certain π-aromatic circuits are enabled, resulting in a more aromatic fullerene than that of C₆₀ , but lower than that of the spherical aromatic C₆₀ ^6- fulleride. Notably, under a field aligned with the saturated carbon atoms, nonaromatic characteristics are exposed. This reveals that spherical-like cages can involve a complex magnetic response that heavily depends on the orientation of the applied field.