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

Switching hydrogen bonding to π-stacking: The thiophenol dimer and trimer Saragi, Rizalina Tama Juanes San José, Marcos Pérez Cuadrado, Cristobal Pinacho Morante, Pablo Tikhonov, Denis S. Caminati, Walther Schnell, Melanie Lesarri Gómez, Alberto Eugenio Hydrogen bondings Enlaces de hidrógeno Pi-stacking Apilamiento Thiophenol Tiofeno 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) 2021-07-30T08:07:33Z 2021-07-30T08:07:33Z 2021 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion 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 eng https://pubs.acs.org/doi/10.1021/acs.jpclett.0c03797 Attribution-NonCommercial-NoDerivatives 4.0 Internacional info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ © 2021 ACS Publications application/pdf ACS Publications https://uvadoc.uva.es/bitstream/10324/47827/2/Switching-hydrogen-bonding.pdf.jpg Hispana TEXT http://creativecommons.org/licenses/by-nc-nd/4.0/ UVaDOC. Repositorio Documental de la Universidad de Valladolid https://uvadoc.uva.es/handle/10324/47827