Identification and quantification of local antiaromaticity in polycyclic aromatic hydrocarbons (PAHs) based on the magnetic criterion.

Abstract

The spatial magnetic properties, through-space NMR shieldings (TSNMRSs, actually the ring current effect in 1H NMR spectroscopy), of a selection of entirely antiaromatic and aromatic polycyclic conjugated hydrocarbons (PCHs), and aromatic PCHs with antiaromatic components, have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. Using both in-plane and above/below-plane ICSS data, polycyclic aromatic hydrocarbons can be readily distinguished from polycyclic antiaromatic ones, even when antiaromatic components are present in the polycyclic aromatic hydrocarbons (PAHs). These antiaromatic zones can also be attributed to internal components of the in-plane deshielding belt present in aromatic compounds and possible partial antiaromatic ring current effects in the same place. This makes it possible to unequivocally confirm correctly assigned or adjust incorrectly assigned antiaromaticity of individual rings in the same molecule.