Journal of Physical Chemistry A, Vol.118, No.7, 1258-1266, 2014
Constrained Clar Formulas of Coronoid Hydrocarbons
Aromatic character of coronoid hydrocarbons is greatly influenced by the shapes of outer and inner peripheries. The most aromatic rings in coronoids are jutting benzene rings on the armchair edges, if any. Clar formulas of many coronoids conform to the aromaticity patterns. However, placement of all aromatic sextets on highly aromatic rings is sometimes forbidden by the presence of the central cavity. The magnitude of aromatic stabilization energy due to macrocyclic conjugation [SSE(mc)] and the NICS(1) value at the center of the cavity strongly depend on the structure of the superposed Clar formula. Localization of pi-electrons in fixed aromatic sextets effectively suppresses macrocyclic conjugation. The sign of SSE(mc) is determined by the number of carbon atoms that form the hub cycle.