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Experimental and computational evidence of halogen bonds involving astatine

Abstract

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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Fig. 1: Side view of the molecular electrostatic potential for AtI calculated at the B3LYP/AVDZ level of theory.
Fig. 2: Distribution of astatine species between the organic and aqueous phases in the presence of (BuO)3PO.
Fig. 3: Distribution of astatine species between the organic and aqueous phases in the presence of Et2S.
Fig. 4: Relationship between XB equilibrium constants.
Fig. 5: Compared evolutions of experimental and computational KBAtI values for six XB acceptors.

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Acknowledgements

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.

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N.Guo, J.C., D.T., J.G., R.M. and G.M. conceived and performed the experimental study. D.T., R.M., J.G. and N.Galland conceived and performed the computational studies. All authors jointly discussed the results and their interpretation, and participated in writing the manuscript.

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Correspondence to Gilles Montavon or Nicolas Galland.

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Supplementary Figures 1–4,Tables 1 and 2and  Structures 1–3

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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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