Switching Hydrogen Bonding to π-Stacking: The Thiophenol Dimer and Trimer.

ABSTRACT: We used jet-cooled broadband rotational spectroscopy to explore the balance between π-stacking and hydrogen-bonding interactions in the self-aggregation of thiophenol. Two different isomers were detected for the thiophenol dimer, revealing dispersion-controlled π-stacked structures anchored by a long S-H···S sulfur hydrogen bond. The weak intermolecular forces allow for noticeable internal dynamics in the dimers, as tunneling splittings are observed for the global minimum. The large-amplitude motion is ascribed to a concerted inversion motion between the two rings, exchanging the roles of the proton donor and acceptor in the thiol groups. The determined torsional barrier of B₂ = 250.3 cm^-1 is consistent with theoretical predictions (290-502 cm^-1) and

SUBMITTER: Saragi RT 

PROVIDER: S-EPMC8812119 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature