The importance of halogen bonds—highly directional interactions between an electron-deficient σ-hole moiety in a halogenated compound and an acceptor such as a Lewis base—is being increasingly recognized in a wide variety of fields from biomedicinal chemistry to materials science. The heaviest halogens are known to form stronger halogen bonds, implying that if this trend continues down the periodic table, astatine should exhibit the highest halogen-bond donating ability. This may be mitigated, however, by the relativistic effects undergone by heavy elements, as illustrated by the metallic character of astatine. Here, the occurrence of halogen-bonding interactions involving astatine is experimentally evidenced. The complexation constants of astatine monoiodide with a series of organic ligands in cyclohexane solution were derived from distribution coefficient measurements and supported by relativistic quantum mechanical calculations. Taken together, the results show that astatine indeed behaves as a halogen-bond donor—a stronger one than iodine—owing to its much more electrophilic σ-hole.
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This work was supported in part by grants from the French National Agency for Research called ‘Investissements d’Avenir’ (ANR-11-EQPX-0004, ANR-11-LABX-0018). The work was carried out using HPC resources from GENCI-CINES/IDRIS (grant 2016-x2016085117) and from CCIPL (Centre de Calcul Intensif des Pays de la Loire). The authors acknowledge the GIP ARRONAX for the production of At-211.
The authors declare no competing interests.
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Guo, N., Maurice, R., Teze, D. et al. Experimental and computational evidence of halogen bonds involving astatine. Nature Chem 10, 428–434 (2018). https://doi.org/10.1038/s41557-018-0011-1
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