Sulfur-centered non-covalent interactions: Emerging themes and challenges from rotational spectroscopy†

Abstract

Non-covalent interactions involving sulfur are linked to a myriad of chemical and biological processes, playing a crucial role in biochemistry, supramolecular chemistry and crystal engineering. However, a precise determination of the energetic and structural properties of these weak, less directional and dispersion-controlled interactions remains a formidable challenge both experimentally and theoretically. In this context, the unique structural sensitivity of microwave spectroscopy is of great significance for the study of jet-cooled clusters, providing a comprehensive molecular description serving as testbed for the computational models. This review highlights recent advancements in the exploration of sulfur-centered non-covalent interactions through rotational spectroscopy. The selected examples emphasize the isotopic-sensitive high-resolution advantage of microwave spectroscopy for the structural and energetic assessment of non-covalent interactions. These insights hold potential to facilitate the understanding and application of such weak interactions within the fields of biochemistry, supramolecular chemistry, and crystal engineering.