Abstract
Halogen bonding (XB) is a type of noncovalent interaction between a halogen atom X in one molecule and a negative site in another. X can be chlorine, bromine or iodine. The strength of the interaction increases in the order Cl<Br<I. After a brief review of experimental evidence relating to halogen bonding, we present an explanation for its occurrence in terms of a region of positive electrostatic potential that is present on the outermost portions of some covalently-bonded halogen atoms. The existence and magnitude of this positive region, which we call the σ-hole, depends upon the relative electron-attracting powers of X and the remainder of its molecule, as well as the degree of sp hybridization of the s unshared electrons of X. The high electronegativity of fluorine and its tendency to undergo significant sp hybridization account for its failure to halogen bond. Some computed XB interaction energies are presented and discussed. Mention is also made of the importance of halogen bonding in biological systems and processes, and in crystal engineering.
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Acknowledgment
We would like to express our gratitude to Professor Jaroslav Burda, who very kindly provided facilities at the Charles University in Prague so that we could prepare this paper while most of us were evacuees from Hurricane Katrina, which hit New Orleans on August 29, 2005.
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Proceedings of “Modeling Interactions in Biomolecules II”, Prague, September 5th–9th, 2005.
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Politzer, P., Lane, P., Concha, M.C. et al. An overview of halogen bonding. J Mol Model 13, 305–311 (2007). https://doi.org/10.1007/s00894-006-0154-7
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DOI: https://doi.org/10.1007/s00894-006-0154-7