Experimental Quantification of Halogen∙∙∙Arene van der Waals Contacts

Andrew West, Nicholas Dominelli Whiteley, Ivan Smoliar, Gary Nichol, Scott L Cockroft

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

Crystallographic and computational studies suggest the occurrence of favorable interactions between polarizable arenes and halogen atoms. However, the systematic experimental quantification of halogen∙∙∙arene interactions in solution has been hindered by the large variance in the steric demands of the halogens. Here we have synthesized molecular balances to quantify halogen∙∙∙arene contacts in 17 solvents and solvent mixtures using 1H NMR spectroscopy. Calculations indicate that favorable halogen∙∙∙arene interactions arise from London dispersion in the gas phase. In contrast, comparison of our experimental measurements with partitioned SAPT0 energies indicate that dispersion is sufficiently attenuated by the solvent that the halogen∙∙∙arene interaction trend was instead aligned with increasing exchange repulsion as the halogen increased in size (ΔGX…Ph= 0 to +1.5 kJ mol-1). Halogen∙∙∙arene contacts were slightly less disfavored in solvents with higher solvophobicities and lower polarizabilities, but strikingly, were always less favored than CH3∙∙∙arene contacts (ΔGMe…Ph= 0 to −1.4 kJ mol−1).
Original languageEnglish
Article numbere202309682
JournalAngewandte Chemie International Edition
Early online date20 Jul 2023
DOIs
Publication statusPublished - 31 Jul 2023

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