Anion⋯Anion (MX3−)2 Dimers (M = Zn, Cd, Hg; X = Cl, Br, I) in Different Environments
Author ORCID Identifier
Rafał Wysokiński https://orcid.org/0000-0002-1133-3535
Wiktor Zierkiewicz https://orcid.org/0000-0002-4038-5959
Mariusz Michalczyk https://orcid.org/0000-0002-6495-6963
Steve Scheiner https://orcid.org/0000-0003-0793-0369
Physical Chemistry Chemical Physics
Royal Society of Chemistry
NSF, Division of Chemistry (CHE) 1954310
NSF, Division of Chemistry (CHE)
The possibility that MX3− anions can interact with one another is assessed via ab initio calculations in gas phase as well as in aqueous and ethanol solution. A pair of such anions can engage in two different dimer types. In the bridged configuration, two X atoms engage with two M atoms in a rhomboid structure with four equal M–X bond lengths. The two monomers retain their identity in the stacked geometry which contains a pair of noncovalent M⋯X interactions. The relative stabilities of these two structures depend on the nature of the central M atom, the halogen substituent, and the presence of solvent. The interaction and binding energies are fairly small, generally no more than 10 kcal mol−1. The large electrostatic repulsion is balanced by a strong attractive polarization energy.
Wysokiński, Rafał, et al. “Anion⋯anion (MX 3 − ) 2 Dimers (M = Zn, Cd, Hg; X = Cl, Br, I) in Different Environments.” Physical Chemistry Chemical Physics, vol. 23, no. 25, 2021, pp. 13853–61. DOI.org (Crossref), https://doi.org/10.1039/D1CP01502H.