Anion Binding Based on Hg3 Anticrowns as Multidentate Lewis Acidic Hosts

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 toward 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 the natural resonance theory and natural bond orbital 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 the molecular orbital theory has allowed us to understand the formation of the pseudo-octahedral second coordination sphere in linear Hg(II) complexes.

Automated summary

In this study, the anion binding capabilities of perfluorinated polymercuramacrocycles were investigated using structural and computational analysis. The coordination preference of these cyclic systems towards specific Lewis bases, both anionic and neutral, were explored using the Cambridge Structural Database (CSD). Interaction energies with different electron-rich species were computed and further analyzed by energy decomposition analysis. Additionally, the natural resonance theory and natural bond orbital analyses were used to understand the key orbitals involved in the interaction and their impact on the final geometry of the adduct. Furthermore, a generalization of the findings using molecular orbital theory provided insights into the formation of the pseudo-octahedral second coordination sphere in linear Hg(II) complexes.