Journal of Physical Chemistry A, Vol.124, No.46, 9611-9616, 2020
Excited-State Aromaticity Reversals in Mobius Annulenes
It is suggested that Mobius annulenes follow a rule similar to Baird's rule such that the 4n and 4n + 2 criteria for Mobius electronic ground-state aromaticity and antiaromaticity are reversed in the lowest triplet and first singlet excited electronic states. Support comes from an investigation of aromaticity in the ground (S-0), lowest triplet (T-1), and first singlet excited (S-1) electronic states of the Mobius-aromatic cyclononatetraenyl cation, C9H9+, using isotropic magnetic shielding isosurfaces calculated with state-optimized complete-active-space self-consistent field wave functions constructed from gauge-including atomic orbitals. Examination of these isosurfaces demonstrates that while the S-0 state of C9H9+ is aromatic, the T-1 and S-1 states are antiaromatic.