Tuning the C–H···π Interaction by Different Substitutions in Benzene–Acetylene Complexes

The influence of substitutions in aromatic moieties on the binding strength of their complexes is a subject of broad importance. Using a set of various substituted benzenes, Sherrill and co-workers ( J. Am. Chem. Soc. 2011 , 133 , 13244 ; J. Phys. Chem. A 2003 , 107 , 8377 ) recently showed that the strength of a stacking interaction (π···π interaction) is enhanced by adding substituents regardless of their nature. Although the binding strength of an activated C-H···π interaction is comparable to that of a stacking interaction, a similar systematic study is hitherto unknown in the literature. We have computed the stabilization energies of the C-H···π complex of acetylene and multiple fluoro-/methyl-substituted benzenes at the coupled-cluster single and double (triple) excitation [CCSD(T)]/complete basis set (CBS) limit. The trend for interaction energies was found to be hexafluorobenzene-acetylene < sym-tetrafluorobenzene-acetylene < sym-trifluorobenzene-acetylene < sym-difluorobenzene-acetylene < benzene-acetylene < sym-dimethylbenzene-acetylene < sym-trimethylbenzene-acetylene < sym-tetramethylbenzene-acetylene < hexamethylbenzene-acetylene. Therefore, contrary to the case of stacking interaction ( Hohenstein et al. J. Am. Chem. Soc. 2011 , 133 , 13244 ), we show here that electron-withdrawing groups weaken the dimer while electron-donating groups strengthen the interaction energy of the dimer. Various recently developed density functional theoretic (DFT) methods were assessed for their performance and the M05-2X, M06-2X, and ωB97X-D methods were found to be the best performers. These best DFT performers were employed in determining the influence of other representative substituents (-NO2, -CN, -COOH, -Br, -Cl, -OH, and -NH2) as an extension to the above work. The results for the complex of acetylene and various para-disubstituted benzenes revealed a trend in binding energies that is in accordance with the ring-activating/deactivating capacity of each of these groups. The stabilization energy was partitioned via the DFT symmetry-adapted perturbation theory (SAPT) method, and both dispersion and electrostatic interactions were seen to be major driving forces for the complex stabilization. Interestingly, the sum of the energy contributors such as dispersion, exchange, induction, etc., is close to zero and the total energy follows the trend of the electrostatic energy. We observe an excellent linear correlation between the optimized intermolecular separation of the different complexes and the exchange/dispersion interaction.