φ-Aromaticity in prismatic {Bi 6 }-based clusters: facts and artifacts

In a recent paper (Peerless et al. Nat. Chem. (2022) https://doi.org/10.1038/s41557-022-01099-5), the authors isolated the heterometallic cluster containing at its heart the prismatic {Bi6}-based cluster and claimed that it is phi-aromatic. Unfortunately, the authors missed the fact that the electronic structure and bonding in the trigonal prisms like {Bi6} have been known for about 30 years, and has nothing to do with aromaticity. In the present Matters Arising comment we demonstrate that the characteristic phi-type molecular orbital - recognized by the authors as bringing aromatic stabilization (and unusual magnetic-response properties) - actually introduces distortion and destabilizes the prism.