Complexes of carbon dioxide with methanol and its monohalogen-substituted: Beyond the tetrel bond

Abstract

This work aims to investigate a significant change in the bonding feature of CO2 complexes that turns from the C∙∙∙O tetrel bond to the OH∙∙∙O hydrogen one due to the effect of halogen-substitution into methanol. The behavior and bonding nature of noncovalent interactions are thoroughly analyzed and discussed. The binding energies were calculated at various methods and extrapolated to the CCSD(T)/CBS. Among DFT-based methods, the B3LYP-D3 is incredibly effective in calculating the binding energy of CH2XOH-CO2 (X = F, Cl, Br) complexes. This work would provide insight into the effect of halogen substituents on the bonding characteristics of noncovalent interactions.