Influence of the Substituents on the CH...π Interaction: Benzene–Methane Complex

Recently we showed that the binding energy of the benzene...acetylene complex could be tuned up to 5 kcal/mol by substituting the hydrogen atoms of the benzene molecule with multiple electron-donating/electron-withdrawing groups (<i>J. Chem. Theory Comput.</i> <b>2012</b>, <i>8</i>, 1935). In continuation, we have here examined the influence of various substituents on the CH...π interaction present in the benzene...methane complex using the CCSD­(T) method at the complete basis set limit. The influence of multiple fluoro substituents on the interaction strength of the benzene...methane complex was found to be insignificant, while the interaction strength linearly increases with successive addition of methyl groups. The influence of other substituents such as CN, NO₂, COOH, Cl, and OH was found to be negligible. The NH₂ group enhances the binding strength similarly to the methyl group. Energy decomposition analysis predicts the dispersion energy component to be on an average three times larger than the electrostatic energy component. Multidimensional correlation analysis shows that the exchange-repulsion and dispersion terms are correlated very well with the interaction distance (<i>r</i>) and with a combination of the interaction distance (<i>r</i>) and molar refractivity (MR), while the electrostatic component correlates well when the Hammett constant is used in combination with the interaction distance (<i>r</i>). Various recently developed DFT methods were used to assess their ability to predict the binding energy of various substituted benzene...methane complexes, and the M06-2X, B97-D, and B3LYP-D3 methods were found to be the best performers, giving a mean absolute deviation of ∼0.15 kcal/mol