Comparison of σ/ π-hole aerogen-bonding interactions based on CH···NgOX (Ng = Kr, Xe; X = F, Cl, Br) complexes.

The geometric structure, energy properties, and electronic properties of the aerogen-bonding interaction formed by CH and NgOX (Ng = Kr, Xe; X = F, Cl, Br) have been studied at the B2PLYP-D3(BJ)/ aug-cc-pVTZ (PP) level. Two kinds of aerogen-bonding interactions were observed among the title systems: the σ-hole and the π-hole complexes. The σ-hole aerogen-bonding complex has a binding energy in the range of - 6.29 ~  - 8.17 kcal/mol, which is the most stable. The binding energies of CH···NgOX increased as X = F < Cl < Br and Ng = KrOX < XeOX for the σ/π-hole aerogen-bonding complexes. The atoms in molecules (AIM), the non-covalent interaction (NCI) index, and the LMO-EDA energy decomposition analysis were adopted to study the nature of the σ/π-hole aerogen-bonding interaction. The results show that the electrostatic term contributes the most to the total interaction energy for the σ/π-hole aerogen-bonding complexes.