Fingerprinting the Nature of Anions in Pyrylium Complexes: Dual Binding Mode for Anion–π Interactions

The interplay between noncovalent interactions that involve oxygenated heteroaromatic rings have been studied for the first time in this work. In particular, we report an advance in knowledge-based anion–π interactions together with (C−H)⁺⋅⋅⋅anion contacts. To understand how the anion modulates these interactions, the synthesis of pyrylium salts with a variety of anions was performed by using an anionic metathesis methodology. The synthesized pyrylium complexes were classified in series, for example, anions derived from halogens, from oxoacids, from p-block elements, and from transition metals. Crystallographic data, DFT calculations, and NMR spectroscopy methods provided access to an overall insight into the noncovalent behavior of the anion in this kind of system. Based on the DFT calculations and ¹H NMR spectroscopy, pyrylium protons can be used as chemical tags to detect noncovalent interactions in this type of compound.