Aromaticity and Antiaromaticity in the Low-Lying Electronic States of Cyclooctatetraene

Abstract

The levels of aromaticity of the most important geometries on the ground-state (S(0)), lowest triplet-state (T(1)), and first singlet excited-state (S(1)) potential energy surfaces (PESs) for cycloocta-1,3,5,7-tetraene (COT) are assessed using a wide range of magnetic criteria including nucleus-independent chemical shifts (NICSs), proton shieldings, and magnetic susceptibilities calculated using complete-active-space self-consistent-field (CASSCF) wave functions constructed from gauge-including atomic orbitals (GIAOs). It is shown that the ground state of D(8h) COT (transition state for the pi-bond-shift process on the S(0) PES) is markedly antiaromatic, even more so than the classical example of an antiaromatic system, the ground state of square cyclobutadiene. The CASSCF-GIAO magnetic properties of the ground state of D(4h) COT (transition state for the ring-inversion process on the S(0) PES) strongly suggest that it is much less antiaromatic than the ground state of D(8h) COT, whereas those of the ground state of D(2d) COT (local minimum on the S(0) PES) indicate that it is decidedly nonaromatic. The lowest triplet state and the first singlet excited state of D(8h) COT (local minima on the T(1) PES and the S(1) PES, respectively) exhibit surprisingly similar magnetic properties. These, in turn, are very close to the magnetic properties of benzene, which is a strong indication of a high degree of aromaticity.