The enhancing effect of a cation-π interaction on the cooperativity of halogen bonds: A computational study

In this work, we investigate the effect of a cation-π interaction on the cooperativity of X⋯N halogen bonds in PhX⋯NCX⋯NH₃ complexes, where Ph=phenyl and X=Cl, Br, I. Molecular geometries and interaction energies of the resulting complexes are studied at the MP2/aug-cc-pVDZ(-PP) computational level. The mechanism of the cooperativity between halogen bonds is analyzed using parameters derived from the noncovalent index, quantum theory of atoms in molecules and natural bond orbital methodologies. It is found that the divalent cations (Be²⁺, Mg²⁺) have a larger influence on the cooperativity of halogen bonds than monovalent ones (Li⁺, Na⁺). The formation of a cation-π interaction leads to strengthening of the halogen bonds, hence increases their cooperativity.