General rules for predicting the local aromaticity of carbon polyhedra

Highlights: • Both the global and local aromaticity of 173 kinds of C₂₄ fullerene isomers are analyzed. • General rules for predicting the local aromaticity of fullerenes are proposed. • In the hexaanionic state, pentagon pair sites exhibit larger local aromaticity. • The square–heptagon bond has a large destabilizing effect on fullerenes. The aromaticity of classical and nonclassical C₂₄ fullerene isomers and their anions were studied using the topological resonance energy (TRE) method. Local aromaticity was studied using the bond resonance energy (BRE) method. On the basis of BRE values, the contributions of different types of chemical bonds to the molecular global aromaticity were analyzed and general rules for predicting the local aromaticity of fullerenes are proposed. It was found that pentagons, heptagons, and squares preferred hexagons as neighbors rather than squares as neighbors. In the hexaanionic state, pentagon pair sites exhibit larger local aromaticity than other places in the same molecule.