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 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.

A 1:1 flavone cocrystal with cyclic trimeric perfluoro-o-phenylenemercury

“…Macrocyclic trimeric perfluoro-o-phenylenemercury [TPPM, (o-C 6 F 4 Hg) 3 ] Lewis acid containing three Hg atoms in a planar nine-membered cycle has been used successfully in recent decades as a multidentate Lewis acid host. Numerous studies registered an excellent oxo-and thiophilicity of this strong electron acceptor manifested in its reactions with various anions and neutral Lewis bases to give complexes wherein the Lewis bases were easily cooperatively coordinated by multiple TPPM binding sites (King et al, 2002a,b;Tikhonova et al, 2005;Castan ˜eda et al, 2015Castan ˜eda et al, , 2016Loveday et al, 2022). In particular, the oxophilicity of TPPM is welldocumented, and the reported examples revealed variable molar ratios and packing arrangements of the TPPM acceptor and O-containing Lewis bases in the crystals (King et al, 2002a,b;Tikhonova et al, 2005;Castan ˜eda et al, 2016).…”

Host–guest chemistry of tridentate Lewis acids based on tribenzotriquinacene

“…Besides mercury, 4 c ,6 silicon 2 d ,7 and tin, 2 e ,3 e ,4 d the elements of the third main group (B, 2 b , c ,3 b , d ,5 b , c ,8 Al, 9 Ga, 10 In 11 ) are often used as acceptor sites. Today, there are various examples of organic backbones with different properties of the resulting PLAs.…”