The principle underlying antiaromaticity

TL;DR

This paper uncovers a fundamental symmetry-based principle linking antiaromaticity with structural instability, small HOMO-LUMO gaps, and paramagnetic currents, demonstrated through molecular examples.

Contribution

It establishes a strict symmetry-induced relation underlying antiaromaticity, connecting molecular distortion, electronic properties, and magnetic response.

Findings

First-order Jahn-Teller distorted molecules exhibit paramagnetic susceptibility.

The principle is exemplified in molecules like cyclobutadiene and pentalene.

A new perspective on antiaromaticity based on symmetry is proposed.

Abstract

Aromaticity is one of the most widely used chemical concepts. Current definitions are purely phenomenological and relate symmetry, reactive stability and the occurence of molecular diamagnetic response currents. The antithetical concept of antiaromaticity provides a connection between the contrary properties of structural instability or distortion out of higher symmetry, a small HOMO-LUMO gap, and paramagnetic response currents. We reveal the principle that is underlying antiaromaticity in showing an intimate and strict symmetry induced relation between these properties. This principle can be proven and is formulated like: First order (and related) Jahn-Teller distorted molecules out of non-isometric point groups are prone to paramagnetic current susceptibility parallel to the main axis of symmetry. We show by the exemplary cases of cyclobutadiene, cylcooctatetraene, pentalene and manganese trifluoride how this principle works and discuss this new perspective on antiaromaticity.