How Globally Aromatic Are Six-Porphyrin Nanorings?

A recent Research Article published in this journal by Matito and coworkers claimed that none of the oxidation states of a butadiyne-linked six-porphyrin nanoring exhibit global aromaticity or antiaromaticity. Here we show that this conclusion is incorrect. A combination of density functional theory (DFT) calculations and experimental NMR data provides compelling evidence for global (anti)aromaticity in a variety of six-porphyrin nanorings in their 2+, 4+ and 6+ oxidation states. The strength of the predicted ring current depends on the choice of DFT functional, so it is crucial to use a functional that reproduces the experimental 1H NMR chemical shifts in these cations.