Unveiling the Sulfur–Sulfur Bridge: Accurate Structural and Energetic Characterization of a Homochalcogen Intermolecular Bond

open 12 si MIUR “PRIN 2015” funds (Grant Number 2015F59J3R) By combining rotational spectroscopy in supersonic expansion with the capability of state-of-the-art quantum-chemical computations in accurately determining structural and energetic properties, the genuine nature of a sulfur–sulfur chalcogen bond between dimethyl sulfide and sulfur dioxide has been unveiled in a gas-jet environment free from collision, solvent and matrix perturbations. A SAPT analysis pointed out that electrostatic S⋅⋅⋅S interactions play the dominant role in determining the stability of the complex, largely overcoming dispersion and C−H⋅⋅⋅O hydrogen-bond contributions. Indeed, in agreement with the analysis of the…