Substituent effects in halogen bonding complexes between aromatic donors and acceptors: a comprehensive ab initio study

Substituent effects in halogen bonding complexes involving aromatic rings are investigated. We have analyzed how the interaction energy (the RI-MP2/aug-cc-pVDZ level of theory) is affected by the substitution in both halogen bond donor and acceptor aromatic moieties. In addition, we have used two different aromatic electron donor molecules pyridine and cyanobenzene, which allow us to study the effect of having the electron donor nitrogen atom forming part of the ring or outside the ring (-CN). Interestingly, the effect of the substituents on the interaction energies is similar in both cases. We have obtained the Hammett's plots for four combinations of aromatic donors and acceptors and in all cases we have obtained good regression plots (interaction energies vs. Hammett's sigma parameter). We have also studied and compared bifurcated halogen bonds using both possible combinations, that is two donors and one acceptor and vice versa. In addition, we have analyzed the effect of the solvent on the interaction energies using COSMO. Finally, we have used Bader's theory of "atoms-in-molecules" to demonstrate that the electron density computed at the bond critical point that emerges upon complexation can be used as a measure of bond order in this noncovalent interaction.