Chapter 4 - A combined theoretical and CSD perspective on σ-hole interactions with tetrels, pnictogens, chalcogens, halogens, and noble gases

Abstract

Compounds incorporating elements belonging to groups 14–18 as electron-deficient sites are capable to establish directional interactions with a variety of Lewis bases (e.g., lone pairs, π-clouds, anions). These noncovalent interactions are usually named as σ/π-hole tetrel (group 14), pnictogen (group 15), chalcogen (group 16), halogen (group 17), and noble gas (or aerogen) bonding (group 18). In general, σ/π-hole interactions offer differentiating energetic and geometric features, and we focus on σ-hole interactions. The differentiating features depend first and foremost on the group and row of the Periodic Table that the element belongs to and can be tuned by its chemical context. This chapter combines insights from theory with solid-state structure evidence to emphasize the similarities and differences among tetrel, pnictogen, chalcogen, halogen, and noble gas bonding σ-hole interactions.