Site specificity of halogen bonding involving aromatic acceptors

Abstract

Halogen bonding (XB) has become one of the most studied non-covalent interactions in the past two decades, owing to its wide range of applications in materials and biological applications. Most of the current theoretical and experimental studies focus on XB involving lone-pair acceptors due to its predictability in terms of crystal geometries. However, recent reports have advocated the importance of XB materials involving aromatic-type acceptors because of their relevance in functional materials, catalysis and biological systems. Herein, we report the XB site-specificity in several polycyclic aromatic hydrocarbons (PAHs) and N-heteroaromatic compounds that are ubiquitous in chemical systems. Based on a series of quantum chemical studies of Cl₂ and Br₂ XB complexes with 14 representative systems, these XB sites can be easily predicted using occupied molecular orbitals and atomic charges. We envisage that the predicted site maps will be useful for materials and drug design involving this class of non-covalent interactions.