Bond length alternation and aromaticity in large annulenes

Properties of [4n] and [4n + 2]annulenes were studied as a function of n for up to [66]annulene using Hartree-Fock and density functional theory in the generalized gradient approximation (DFT-GGA). In the 4n + 2 series a "transition" from delocalized to localized structures occurs at 4n + 2 = 30. Various indices of aromaticity, including NMR chemical shifts, bond localization, and aromatic stabilization energy (ASE) were monitored. pi-bond localization occurs not due to a dramatic decrease of ASE as n increases, but rather as a result of a pseudo-Jahn-Teller (PJT) effect that sets in as the HOMO-LUMO gap decreases with increasing size. The NMR measures of aromaticity (difference between inner and outer H-1 chemical shielding constants and the nucleus-independent chemical shifts, NICS) are reduced in the localized structures in comparison to the delocalized ones. The gradual nature of this "transition" is also implied by the relatively large values of the NMR measures of aromaticity that approach zero only gradually for larger size annulenes. Therefore intermediate size annulenes, such as [30]annulene are predicted to have a localized structure and aromatic properties at the same time showing the delocalized structure is not a necessary condition to be aromatic. (C) 1998 American Institute of Physics.