2026-04-27T22:07:25Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/478272025-09-04T11:48:53Zcom_10324_28542com_10324_952com_10324_894col_10324_28543

Saragi, Rizalina Tama Juanes San José, Marcos Pérez Cuadrado, Cristobal Pinacho Morante, Pablo Tikhonov, Denis S. Caminati, Walther Schnell, Melanie Lesarri Gómez, Alberto Eugenio 2021-07-30T08:07:33Z 2021-07-30T08:07:33Z 2021 The Journal of Physical Chemistry Letters, 2021, vol. 12, n. 5. p. 1367-1373 1948-7185 https://uvadoc.uva.es/handle/10324/47827 10.1021/acs.jpclett.0c03797 Producción Científica 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. Ministerio de Ciencia e Innovación - Fondo Europeo de Desarrollo Regional (grant PGC2018-098561-BC22) Deutsche Forschungsgemeinschaft (grant SCHN1280/4-2) application/pdf eng ACS Publications info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2021 ACS Publications Attribution-NonCommercial-NoDerivatives 4.0 Internacional Hydrogen bondings Enlaces de hidrógeno Pi-stacking Apilamiento Thiophenol Tiofeno Switching hydrogen bonding to π-stacking: The thiophenol dimer and trimer info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion https://pubs.acs.org/doi/10.1021/acs.jpclett.0c03797 SI