Anion binding based on Hg3 anticrowns as multidentate Lewis acidic hosts

Abstract

We present herein a combined structural and computational analysis of the anion binding capabilities of perfluorinated polymercuramacrocycles . The Cambridge Structural Database (CSD) has been explored to find the coordination preference of these cyclic systems towards specific Lewis bases, both anionic and neutral. Interaction energies with different electron rich species have been computed and further decomposed into chemically meaningful terms by means of energy decomposition analysis. Furthermore, we have investigated, by means of NRT and NBO analyses how the orbitals involved in the interaction are key in determining the final geometry of the adduct. Finally, a generalization of the findings in terms of molecular orbital theory has allowed us to understand the formation of the pseudo-octahedral second coordination sphere in linear Hg(II) complexes.