Anion-π Interactions: What's in the Name?

The studies of the anion-π interactions advanced during the last two decades from the discussion of the mere existence of this counter-intuitive bonding to its utilization for anion recognition and transport, catalysis, and other applications. Yet, there are substantial differences in the interpretation of nature and the driving forces of anion-π bonding. Most surprisingly, there are still different opinions about the meaning of this term (i. e., which associations can be considered anion-π complexes). After a brief overview of the studies in this area (including early examples of such complexes), we suggested that anion-π bonding occurs when there is evidence of a net attraction between a (close-shell) anion and the face of an electrophilic π-system. This definition encompasses fundamentally similar supramolecular complexes comprising diverse π-systems and anions and its general acceptance would facilitate a discussion of the nature and distinct driving forces of this fascinating interaction.