Computational insights into halogen bonding between PCl contact and several electron donors

Abstract

AbstractIn this work, computations of density functional theory (DFT) have been carried out to investigate the interactions between the PCl unit of hexachlorocyclotriphosphazene and several common electron donors. Such small systems are selected to explore the potential P‐bound halogen bonding interactions within polymeric structure and supramolecules. In all cases, the intermolecular distances are shown to be equal to or below sums of van der Waals radii of the atoms involved. Halogen bonding energies, calculated at B971/6‐311+G(d,p), span over a relatively lager range, from −0.95 to −95.30 kcal/mol, which intimate that the interactions are comparable to, or even partly prevail over, the conventional hydrogen bonding. For the charge‐assisted systems, calculations show that these systems can result in much stronger halogen bonding than the corresponding neutral ones. The results agree well with those of natural population analysis (NPA). Finally, the theory of atoms in molecules (AIM) was applied to provide more insight into the nature of these interactions. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010