The halogen bond: an interim perspective

There has been an upsurge of interest in the halogen bond during the last decade. This non-covalent interaction is less familiar than the hydrogen bond, but is similar to it in several respects. In this article, we first discuss the nature of the halogen bond in the gas phase, as established by systematic investigations of the rotational spectra of complexes B...XY, where B is a simple Lewis base and XY is a dihalogen molecule. The geometry of a given B...XY is found to be isomorphic with that of the corresponding hydrogen-bonded system B...HX, an observation that leads an interim definition of the halogen bond similar to that recently proposed for the hydrogen bond. Selected novel applications of the halogen bond made in the last decade in various areas of chemistry/materials (namely crystal engineering, liquid crystals, nano-materials, polymer chemistry and inorganic chemistry) are then reviewed. These applications generally involve molecules of the type XR (where R is an electron-withdrawing group) acting as the electron donor, rather than dihalogens XY.