Structure prediction and aromaticity of acenes and phenylenes series. A combination method between asymmetric Kekulé structures

Abstract

The combination method between asymmetric Kekulé structures (CMAK) was expanded to the structure prediction of a series of acenes and phenylenes. The structures predicted by the CMAK correspond to those calculated by the ab initio molecular orbital (MO) and B3LYP density functional methods. The CMAK can characterize the structures. The aromaticity for the whole ring and each ring in the treated compounds was estimated by the index of deviation from aromaticity (IDA). The estimated aromaticity corresponds fairly well to the characterization of the structure predicted by the CMAK. The predicted structures of linear acenes reveal the aromaticity of the central ring and also explain its reactivity. The side ring in [n]phenacene shows high aromaticity. The critical difference in the structure and aromaticity for the central six‐membered ring of the isomers benzo[1,2:4,5]dicyclobutene and benzo[1,2:5,6]dicyclobutene was explained. Copyright © 2012 John Wiley & Sons, Ltd.