Halogen bonding: from self-assembly to materials and biomolecules

William T. Penningtona, Giuseppe Resnatib and Mark S. Taylorc
aDepartment of Chemistry, Clemson University, Clemson, SC, USA. E-mail: billp@clemson.edu; Fax: +1 864-656-6613; Tel: +1 864-656-4200
bDepartment of Chemistry, Materials and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, 20131 Milan, Italy. E-mail: giuseppe.resnati@polimi.it; Fax: +39 022399 3180; Tel: +39 022399 3032
cDepartment of Chemistry, University of Toronto, Toronto, ON, Canada. E-mail: mtaylor@chem.utoronto.ca; Fax: +1 416-978-8775; Tel: +1 416-946-0571

Halogens are versatile substituents in supramolecular chemistry, displaying the ability to participate in noncovalent interactions with both electron-deficient and electron-rich partners. Interactions with Lewis basic species – in apparent contradiction of the general depiction of halogens as sites of electron density – are known as halogen bonds. An IUPAC task group has recently advanced the following definition: “A halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity.”1

Crystallography has played a central role in the study of halogen bonding since Nobel laureate Odd Hassel's seminal work on the co-crystals of Lewis bases with molecular halogens, interhalogens, and halocarbons.2 Data from the solid state have been invoked as key evidence for the existence and the generality of this phenomenon, and have informed current thought regarding the directionality and strengths of the interactions. Over the past 10–15 years, there have been remarkable increases in both the scope of research on halogen bonding in the solid state and the range of applications that have been demonstrated.3

The articles collected in this themed issue of CrystEngComm reflect the diverse directions of current research on halogen bonding. Topics discussed include: computational and spectroscopic studies of the geometries and thermodynamics of halogen bonding interactions; pnictogen and chalcogen bonding, the group 15 and 16 ‘siblings’ of halogen bonding; demonstrations of the utility of halogen bonding as a motif for crystal engineering of organics and metal complexes; and applications of the interaction in directing the solid-state organization of semiconductive and magnetic materials.

We thank the authors for contributing their work to this issue, as well as the editorial team for their dedication and assistance in bringing it about. We hope that this collection of articles will play a role in stimulating further work on fundamental aspects and new applications of these fascinating interactions.

Notes and references

  1. G. R. Desiraju, P. S. Ho, L. Kloo, A. C. Legon, R. Marquardt, P. Metrangolo, P. A. Politzer, G. Resnati and K. Risannen, “Definition of the Halogen Bond”,  Search PubMedhttp://www.iupac.org/nc/home/projects/project-db/project-details.html?tx_wfqbe_pi1%5bproject_nr%5d=2009-032-1-100.
  2. O. Hassel, Science, 1970, 170, 497–502 CAS.
  3. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati and G. Terraneo, Angew. Chem., Int. Ed., 2008, 47, 6114–6127 CrossRef CAS.

This journal is © The Royal Society of Chemistry 2013
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