Taming XeO₃ with Aza-Crowns: Computational Studies into σ-Hole Mediated Host-Guest Interactions

Various aza-crowns with different sizes and substituents have been explored computationally as potential hosts for stabilizing the explosive guest xenon trioxide (XeO₃) through σ-hole-mediated aerogen bonding interactions. Interestingly, aza-crowns demonstrate superior binding towards XeO₃ compared to their oxygen and thio counterparts. However, unlike the latter cases, where the binding was found to be increasingly favorable with the increase in the size of the crowns, aza-crowns exhibit a variable size preference for XeO₃, peaking with aza-15-crown-5, and reducing thereafter with increase in crown size.