Aromaticity Switching by Quantum Tunnelling

Abstract

Antiaromatic π-conjugated systems provide a powerful framework for understanding ultrafast molecular rearrangements driven by quantum tunnelling over their degenerate double-well potential surfaces. Here, we explore with computational tools the π-bond-shifting automerization in the antiaromatic Dinaphtho[2,1-a:1,2-f]pentalene (1), Dinaphtho[1,2-a:2,1f]pentalene (2), and a series of substituted derivatives. These molecules exhibit a distinctive feature: local aromatic and antiaromatic rings can interconvert their aromaticity character even close to the absolute zero via unusually fast carbon tunnelling. If these systems can be prepared in a coherent regime, the quantum superposition between the original states would delocalise their nuclear wavefunctions in a state that we describe as a "Schrödinger's aromaticity cat."