Localisation and reversal of paratropic ring currents in molecules with formal anti-aromatic electron counts

Abstract

The aromatic character of the six smallest members of the α,ω-bicyclopentadiene-polyacene series (1(n)) has been assessed using magnetic and energetic criteria. Current density maps (CTOCD-DZ/6-31G**//B3LYP/6-31G**) show that, along the series, the ring current changes from paratropic in pentalene (1(0)) and s-indacene (1(1)), through quenched in 1(2) and 1(3), to diatropic in 1(4) and 1(5). These changes are rationalised in terms of orbital contributions to current. Valence bond calculations (VB/6-31G//B3LYP/6-31G**) in which the π system is composed of strictly atomic p-orbitals, show that the electronic structures in these homologous series can be described in terms of the two closed-shell Kekulé resonance structures for the smallest molecules, but that in the larger molecules allyl-polyacene-allyl biradical structures prevail, owing to the larger resonance energies. This trend in electronic structure parallels the switch from paratropic to diatropic character.