The aromatic character of the six smallest members of the of alpha,omega-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 pi 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 Kekule 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.

Localisation and reversal of paratropic ring currents in molecules with formal anti-aromatic electron counts / Rwa, Havenith; Jj, Engelberts; Pw, Fowler; E., Steiner; JH van, Lenthe; Lazzeretti, Paolo. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - STAMPA. - 6(2004), pp. 289-294.

I documenti presenti in Iris Unimore sono rilasciati con licenza Creative Commons Attribuzione - Non commerciale - Non opere derivate 3.0 Italia, salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Powered by IRIS-about IRIS-Utilizzo dei cookie

 Copyright © 2021