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Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts

Nature Chemistry volume 6, pages 1039–1043 (2014)Cite this article

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Abstract

Halogen bonding (XB), the attractive interaction between an electron-deficient halogen atom and a Lewis base, has undergone a dramatic development as an intermolecular force analogous to hydrogen bonding (HB). However, its utilization in the solution phase remains underdeveloped. Furthermore, the design of receptors capable of strong and selective recognition of anions in water remains a significant challenge. Here we demonstrate the superiority of halogen bonding over hydrogen bonding for strong anion binding in water, to the extent that halide recognition by a simple acyclic mono-charged receptor is achievable. Quantification of iodide binding by rotaxane hosts reveals the strong binding by the XB-rotaxane is driven exclusively by favourable enthalpic contributions arising from the halogen-bonding interactions, whereas weaker association with the HB-rotaxanes is entropically driven. These observations demonstrate the unique nature of halogen bonding in water as a strong alternative interaction to the ubiquitous hydrogen bonding in molecular recognition and assembly.

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Figure 1: Anion recognition in water using halogen bonding.
Figure 2: Chloride anion-templated synthesis of HB and XB rotaxane anion receptors.
Figure 3: Anion binding titrations with XB rotaxane 4 in D2O.
Figure 4: Amide-functionalized HB-donating anion receptors.
Figure 5: MD simulation of 4 with I–.

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Acknowledgements

M.J.L. thanks the Engineering and Physical Sciences Research Council (EPSRC) for a Doctoral Training Account (DTA) studentship. S.W.R. thanks the Clarendon Fund and St. John's College, Oxford, for financial support. I.M. thanks the Fundação para a Ciência e a Tecnologia (FCT) for PhD scholarship SFRH/BD/87520/2012.

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Authors and Affiliations

  1. Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK

    Matthew J. Langton, Sean W. Robinson & Paul D. Beer

  2. Departamento de Química, CICECO and Secção Autónoma de Ciências da Saúde, Universidade de Aveiro, Aveiro, 3810-193, Portugal

    Igor Marques & Vítor Félix

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Contributions

P.D.B. conceived the project. The experimental work was performed mainly by M.J.L., with contributions from S.W.R. towards the synthesis of 1 and 2. I.M. and V.F. conducted the theoretical calculations. All authors contributed to the analysis of the data. M.J.L. and P.D.B. wrote the paper, with assistance from S.W.R. and V.F.

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Correspondence to Paul D. Beer.

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Langton, M., Robinson, S., Marques, I. et al. Halogen bonding in water results in enhanced anion recognition in acyclic and rotaxane hosts. Nature Chem 6, 1039–1043 (2014). https://doi.org/10.1038/nchem.2111

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