The Clar aromatic sextet theory can provide a qualitative description of the dominant modes of cyclic π-electron conjugation in benzenoid molecules and of the relative stability among a series of isomeric benzenoid systems. In a series of nonplanar fully benzenoid hydrocarbons, the predictions of the Clar theory were tested by means of several different theoretical approaches: topological resonance energy (TRE), energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six center delocalization index (SCI), and nucleus-independent chemical shifts (NICS). To assess deviations from planarity in the examined molecules, four different planarity descriptors were employed. It was shown how the planarity indices can be used to quantify the effect of nonplanarity on the local and global aromaticity of the studied systems.

A detailed analysis of the local aromaticity in tetraoxa[8]circulene and its benzo-annelated derivates was performed by means of the energy effect (ef), multicenter delocalization indices (MCI), harmonic oscillator model of aromaticity (HOMA) index, nucleus independent chemical shifts (NICS), and ring current maps. According to the indices employed, the central ring of tetraoxa[8]circulene is antiaromatic, whereas the benzenoid and furanoid rings are aromatic. The calculated current density distribution in tetraoxa[8]circulenes showed that the "annulene within an annulene" model of aromaticity is not applicable for these compounds. It was found that the presence of benzo-annelated rings enhances (respectively diminishes) aromaticity (respectively antiaromaticity) of the five-membered (respectively eight-membered) rings in tetraoxa[8]circulenes. These effects are found to be proportional to the number of benzo-annelated rings. The observed regularities can be rationalized by means of the pairwise energy effect (pef) of cyclic conjugation.

Local aromaticity in rings of conjugated hydrocarbons can be measured in a variety of ways. In the present paper, we concentrate on two of these, namely, EC, i.e., the pi-electron content or pi-electron partition, and ef, the energy effect of cycles. For the central ring in five bipartite conjugated hydrocarbons (anthracene, triphenylene, perylene, coronene, and biphenylene), it was found that EC and ef values are modified in a consistent and predictable manner by annelation with benzenoid rings. Equations are presented for computing EC and ef values for the central ring in terms of three integers representing the numbers of annelated benzenoid rings (A, L, and G for angular, linear, and geminal annelation, respectively). The coefficients of A and G are positive (A > G) and the coefficient of L is negative for benzenoids, but for biphenylene, the situation is reversed for coefficients in the correlation for ef values.

The effect of benzo-annelation on the local aromaticity of the central ring of acridine (1), 9H-carbazole (2), dibenzofuran (3), and dibenzothiophene (4) was analyzed by means of the energy effects (ef), pairwise energy effects (pef), multicenter delocalization index (MCI), electron density at ring critical points (ρ(r(C))), harmonic oscillator model of aromaticity (HOMA), and nucleus independent chemical shifts (NICS). According to energetic, electron delocalization, and geometrical indices, angular benzo-annelation increases, whereas linear benzo-annelation decreases, the extent of the local aromaticity of the central ring containing heteroatoms. The local aromaticity of the central heterocyclic ring in the examined molecules can significantly vary by applying different modes of benzo-annelation. The NICS values do not always support the results obtained by the other aromaticity indices and, in some cases, lead to completely opposite conclusions.

All Kekulé-structure-based theories predict that the central five-membered ring in fluoranthene and naphtho-annelated fluoranthenes is nonaromatic. In the present work, a detailed study of the local aromaticity in a series of naphtho-annelated fluoranthene derivatives was performed by means of the following aromaticity indices: the energy effect (ef), bond resonance energy (BRE), multicenter delocalization indices (MCI), harmonic oscillator model of aromaticity (HOMA) index, nucleus-independent chemical shifts (NICS), and ring current maps. It was found that, according to the ef, BRE, MCI, and HOMA values, the pentagonal rings in some naphtho-annelated fluoranthenes can be even more aromatic than some hexagonal rings in the respective molecules. The magnetic indices do not support the results obtained by the energetic, electron delocalization, and geometrical aromaticity indices.