Author ORCID Identifier
Anna Grabarz https://orcid.org/0000-0002-3740-0660
Mariusz Michalcyz https://orcid.org/0000-0002-6495-6963
Wiktor Zierkiewicz https://orcid.org/0000-0002-4038-5959
Steve Scheiner https://orcid.org/0000-0003-0793-0369
NSF, Division of Chemistry (CHE) 1954310
NSF, Division of Chemistry (CHE)
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This work is licensed under a Creative Commons Attribution 4.0 License.
Ab initio calculations are applied to the question as to whether a AeX5− anion (Ae = Kr, Xe) can engage in a stable complex with another anion: F−, Cl−, or CN−. The latter approaches the central Ae atom from above the molecular plane, along its C5 axis. While the electrostatic repulsion between the two anions prevents their association in the gas phase, immersion of the system in a polar medium allows dimerization to proceed. The aerogen bond is a weak one, with binding energies less than 2 kcal/mol, even in highly polar aqueous solvent. The complexes are metastable in the less polar solvents THF and DMF, with dissociation opposed by a small energy barrier.
Grabarz, A.; Michalczyk, M.; Zierkiewicz, W.; Scheiner, S. Anion–Anion Interactions in Aerogen-Bonded Complexes. Influence of Solvent Environment. Molecules 2021, 26, 2116. https://doi.org/10.3390/molecules26082116