Unveiling the Nature and Strength of Selenium-Centered Chalcogen Bonds in Binary Complexes of SeO 2 with Oxygen-/Sulfur-Containing Lewis Bases: Insights from Theoretical Calculations.

Among various non-covalent interactions, selenium-centered chalcogen bonds (SeChBs) have garnered considerable attention in recent years as a result of their important contributions to crystal engineering, organocatalysis, molecular recognition, materials science, and biological systems. Herein, we systematically investigated π-hole-type Se ∙∙∙ O/S ChBs in the binary complexes of SeO 2 with a series of O-/S-containing Lewis bases by means of high-level ab initio computations. The results demonstrate that there exists an attractive interaction between the Se atom of SeO 2 and the O/S atom of Lewis bases. The interaction energies computed at the MP2/aug-cc-pVTZ level range from -4.68 kcal/mol to -10.83 kcal/mol for the Se ∙∙∙ O chalcogen-bonded complexes and vary between -3.53 kcal/mol and -13.77 kcal/mol for the Se ∙∙∙ S chalcogen-bonded complexes. The Se ∙∙∙ O/S ChBs exhibit a relatively short binding distance in comparison to the sum of the van der Waals radii of two chalcogen atoms. The Se ∙∙∙ O/S ChBs in all of the studied complexes show significant strength and a closed-shell nature, with a partially covalent character in most cases. Furthermore, the strength of these Se ∙∙∙ O/S ChBs generally surpasses that of the C/O-H ∙∙∙ O hydrogen bonds within the same complex. It should be noted that additional C/O-H ∙∙∙ O interactions have a large effect on the geometric structures and strength of Se ∙∙∙ O / S ChBs. Two subunits are connected together mainly via the orbital interaction between the lone pair of O/S atoms in the Lewis bases and the BD*(OSe) anti-bonding orbital of SeO 2 , except for the SeO 2 ∙∙∙ HCSOH complex. The electrostatic component emerges as the largest attractive contributor for stabilizing the examined complexes, with significant contributions from induction and dispersion components as well.