RT info:eu-repo/semantics/article
T1 Switching hydrogen bonding to π-stacking: The thiophenol dimer and trimer
A1 Saragi, Rizalina Tama
A1 Juanes San José, Marcos
A1 Pérez, Cristóbal
A1 Pinacho Morante, Pablo
A1 Tikhonov, Denis S.
A1 Caminati, Walther
A1 Schnell, Melanie
A1 Lesarri Gómez, Alberto Eugenio
K1 Hydrogen bondings
K1 Enlaces de hidrógeno
K1 Pi-stacking
K1 Apilamiento
K1 Thiophenol
K1 Tiofeno
AB 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 the monomer barrier of 277.1(3) cm–1. For the thiophenol trimer, a symmetric top structure was assigned in the spectrum. The results highlight the relevance of substituent effects to modulate π-stacking geometries and the role of the sulfur-centered hydrogen bonds.
PB ACS Publications
SN 1948-7185
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/47827
UL https://uvadoc.uva.es/handle/10324/47827
LA eng
NO The Journal of Physical Chemistry Letters, 2021, vol. 12, n. 5. p. 1367-1373
NO Producción Científica
DS UVaDOC
RD 22-nov-2024