Switching Hydrogen Bonding to π-Stacking: The Thiophenol Dimer and Trimer
| Autor: | Alberto Lesarri, Rizalina Tama Saragi, Cristobal Perez, Walther Caminati, Denis S. Tikhonov, Melanie Schnell, Marcos Juanes, Pablo Pinacho |
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| Rok vydání: | 2021 |
| Předmět: |
Materials science
Letter Astrophysics::High Energy Astrophysical Phenomena Dimer Stacking Tiofeno Trimer 010402 general chemistry 01 natural sciences chemistry.chemical_compound ddc:530 General Materials Science Thiophenol Physics::Atomic Physics Physical and Theoretical Chemistry Pi-stacking 010405 organic chemistry Hydrogen bond Hydrogen bondings Enlaces de hidrógeno Apilamiento 0104 chemical sciences Crystallography chemistry Rotational spectroscopy |
| Zdroj: | The Journal of Physical Chemistry Letters UVaDOC. Repositorio Documental de la Universidad de Valladolid instname The journal of physical chemistry letters 12(5), 1367-1373 (2021). doi:10.1021/acs.jpclett.0c03797 |
| ISSN: | 1948-7185 2018-0985 |
| DOI: | 10.1021/acs.jpclett.0c03797 |
| Popis: | 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) |
| Databáze: | OpenAIRE |
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