Structures, stabilities, and IR and 13C-NMR spectra of dihedral fullerenes: A density functional theory study

Dihedral fullerenes are thermodynamically stable molecules with D (nd) or D (nh) symmetry. Based on experimental findings, two series of dihedral fullerenes with five-fold (C5) and six-fold (C6) symmetry have been studied using density functional theory (DFT). The DFT calculations showed that for both series the stabilities increased with increasing fullerene size. Structural analyses indicated that the stabilities are related to specific local geometries. In the case of the more abundant C5 series, the presence of approximately planar pentagons and hexagons on the top bowl favors their formation. That is to say, those fullerenes with small dihedral angles within the polygons are readily formed, because planar hexagons lead to strengthened conjugation which lowers average bonding energies (ABE) and increases thermodynamic stabilities. Non-planar hexagons at equatorial positions in tube-shaped fullerenes have an adverse effect on the conjugation and inhibit their formation. Calculations also demonstrated that fullerenes in the two series, including C-50(D (5h) ), C-60(D (6h) ), C-80(D (5d) ), C-96(D (6d) ), C-110(D (5h) ), and C-120(D (5d) ), have thermodynamically stable triplet structures with strong conjugation. The calculated IR and C-13 NMR spectra of the fullerenes show some similarities and regular trends due to their homogenous structures. The electronic structures indicate that short double bonds in hexagons with high electron occupancies are readily attacked by electrophilic agents and can also be coordinated by transition metals. Mechanistic discussions suggested that C-2 additions and C-2 losses constitute reversible processes at high temperature and C-2 additions in pentagonal fusions are crucial to the kinetics of the curvature of structures. C-3 additions lead to the formation of large fullerenes of other types.