Delocalised antimony(lone pair)- and bismuth-(lone pair)…π(arene) interactions: Supramolecular assembly and other considerations

• Sb/Bi(lone pair)…π(arene) interactions are found in their molecular compounds.
• Supramolecular aggregation patterns based on Sb/Bi(lone pair)…π(arene) interactions are evident.
• Zero-, one- and two-dimensional architectures may be stabilised by Sb/Bi(lone pair)…π(arene) interactions.

A bibliographic review of the crystallographic literature reveals that Sb(lone pair), Bi(lone pair)…π(arene) interactions, where the lone pair of electrons is projected towards the centre of the arene ring, exist in the crystal structures of antimony(III) and bismuth(III) compounds and that, when operating in isolation of other supramolecular motifs, can stabilise clearly defined zero-, one- and two-supramolecular aggregates. Comparisons of closely related structures reveal systematic trends in the distance between the antimony(III) and bismuth(III) centre and the ring centroid of the interacting arene ring that are correlated with the Lewis acidity of the metal centre or the electronegativity of metal- or arene-bound substituents.

Sb(lone pair)…π(arene) interactions and analogous interactions involving Bi, operating independently of other synthons, are found to mediate the association between molecules in their crystal structures, leading to a 0-, 1- and 2-D supramolecular architectures.Figure optionsDownload high-quality image (250 K)Download as PowerPoint slide