Stabilisation of dianion dimers trapped inside cyanostar macrocycles

Abstract

Interanionic H-bonds (IAHBs) are unfavourable interactions in the gas phase becoming favoured when anions are in solution. Dianion dimers are also susceptible to being trapped inside the cavities of cyanostar (CS) macrocycles, and thus, the formation of 2 : 2 anion : cyanostar aggregates is mainly supported by three kinds of interactions: IAHBs between the dianions, π–π stacking between the confronted cyanostars, and the presence of an intricate network of multiple C(sp²)H⋯O H-bonds between cyanostar ligands and the anionic moieties. An analysis of the interaction energies supported by NBO reveals a slight cooperative effect of the CSs on the IAHB stabilisation.