Comparative investigation of interactions of hydrogen, halogen and tetrel bond donors with electron-rich and electron-deficient π-systems

Abstract

Recently, noncovalent interactions in complexes and crystals have attracted considerable interest. The current study was thus designed to gain a better understanding of three seminal types of noncovalent interactions, namely: hydrogen, halogen and tetrel interactions with π-systems. This study was performed on three models of Lewis acids: X₃–C–H, F₃–C–X and F–T–F₃ (where X = F, Cl, Br and I; and T = C, Si, Ge and Sn) and three π-systems as Lewis bases: benzene (BZN), 1,3,5-trifluorobenzene (TFB) and hexafluorobenzene (HFB). Quantum mechanical calculations, including geometrical optimization, molecular electrostatic potential (MEP), maximum positive electrostatic potential (V_s,max), Point-of-Charge (PoC), potential energy surface (PES), quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) calculations, were carried out at the MP2/aug cc-pVDZ level of theory. The binding energies were additionally benchmarked at the CCSD(T)/CBS level. The results showed that: (i) the binding energies of the X₃–C–H⋯π-system complexes were unexpectedly inversely correlated with the V_s,max values on the hydrogen atom but directly correlated with the X atomic sizes; (ii) the binding energies for the F₃–C–X⋯π-system and F–T–F₃⋯π-system complexes were correlated with the σ-hole magnitudes of the X and T atoms, respectively; and (iii) for the F₃–C–F⋯π-system complexes, the binding energy was as strong as the π-system was electron-deficient, indicating the dominating nucleophilic character of the fluorine atom. NCI analysis showed that the unexpected trend of X₃–C–H⋯π-system binding energies could be attributed to additional attractive interactions between the X atoms in the X₃–C–H molecule and the carbon atoms of the π-system. Furthermore, the I₃–Sn–H molecule was employed as a case study of hydrogen, halogen and tetrel interactions with π-systems. It was found that hydrogen and halogen interactions of the I₃–Sn–H molecule correlated with the electron-richness of the π-system. In contrast, tetrel interactions correlated with the electron deficiency of the π-system.