paratropicity

Paratropicity is a term used in molecular magnetism and aromaticity theory to describe the tendency of a cyclic, conjugated system to sustain a paratropic ring current when exposed to an external magnetic field. This current flows in the opposite direction to the diatropic ring current associated with classic aromatic systems, and it is most closely linked to antiaromatic behavior.

In the framework of Hückel aromaticity, systems with 4n pi electrons are considered antiaromatic and tend to exhibit paratropic ring currents, whereas systems with 4n+2 pi electrons display diatropic currents characteristic of aromaticity. Nonaromatic rings may have weak or negligible ring currents. Paratropicity thus serves as a magnetic criterion for assessing electronic delocalization and potential instability arising from antiaromaticity.

Experimentally, paratropicity is inferred from magnetic properties such as NMR chemical shifts and the overall magnetic susceptibility, as well as from more direct computational analyses. Positive nucleus-independent chemical shift (NICS) values and certain patterns of deshielding around the ring are associated with paratropic (antiaromatic) currents. Computational methods, including anisotropy of the induced current density (ACID) plots, help visualize and quantify paratropic ring currents.

Examples of systems discussed in relation to paratropicity include planar antiaromatic species with 4n pi electrons, which would support paratropic currents if forced into planarity, and real-world structures like tub-shaped cyclooctatetraene that avoid antiaromaticity by distortion. Paratropicity remains a useful concept for interpreting magnetic responses and the degree of antiaromatic character in cyclic conjugated molecules.