Structure Determination, Conformational Flexibility, Internal Dynamics, and Chiral Analysis of Pulegone and Its Complex with Water
dc.contributor.author | Krin, Anna | |
dc.contributor.author | Pérez-Cuadrado, Cristóbal | |
dc.contributor.author | Pinacho, Pablo | |
dc.contributor.author | Quesada-Moreno, María Mar | |
dc.contributor.author | López-González, Juan Jesús | |
dc.contributor.author | Avilés-Moreno, Juan Ramón | |
dc.contributor.author | Blanco-Rodríguez, Susana | |
dc.contributor.author | López-Alonso, Juan Carlos | |
dc.contributor.author | Schnell, Melanie | |
dc.date.accessioned | 2025-01-30T10:19:06Z | |
dc.date.available | 2025-01-30T10:19:06Z | |
dc.date.issued | 2018 | |
dc.description.abstract | In the current work we present a detailed analysis of the chiral molecule pulegone, which is a constituent of essential oils, using broadband rotational spectroscopy. Two conformers are observed under the cold conditions of a molecular jet. We report an accurate experimentally determined structure for the lowest energy conformer. For both conformers, a characteristic splitting pattern is observed in the spectrum, resulting from the internal rotation of the two non-equivalent methyl groups situated in the isopropylidene side chain. The determined energy barriers are 1.961911(46) kJ/mol and 6.3617(12) kJ/mol for one conformer, and 1.96094(74) kJ/mol and 6.705(44) kJ/mol for the other one. Moreover, a cluster of the lowest energy conformer with one water molecule is reported. The water molecule locks one of the methyl groups via a hydrogen bond and some secondary interactions, so that we only observe internal rotation splittings from the other methyl group with an internal rotation barrier of 2.01013(38) kJ/mol. Additionally, the chirality-sensitive microwave three-wave mixing technique is applied for the differentiation between the enantiomers, which can become of further use for the analysis of essential oils. | es_ES |
dc.description.sponsorship | A. K. acknowledges the financial support of the IMPRS-UFAST and the use of the GWDG computing cluster. C. P. acknowledges grant by the Alexander von Humboldt Stiftung. M. M. Q. M. thanks the Universidad de Jaén for a predoctoral fellowship and the Max Planck Society and the Prince of Asturias Foundation for a Max Planck-Prince of Asturias Award Mobility Grant. The authors are also thankful to the Centro de Servicios de Informática y Redes de Comunicaciones (CSIRC), University of Granada (UGR), for computational time and facilities. J. C. L, S. B., and P. P. acknowledge the Ministerio de Economía y Competitividad (Grant CTQ 2016-75253-P) for financial support. P. P. acknowledges the University of Valladolid for a mobility grant. | es_ES |
dc.identifier.citation | Chem. Eur. J. 2018, 24, 721 – 729 | es_ES |
dc.identifier.issn | 0947-6539 | es_ES |
dc.identifier.other | 10.1002/chem.201704644 | es_ES |
dc.identifier.uri | https://hdl.handle.net/10953/4572 | |
dc.language.iso | eng | es_ES |
dc.publisher | Wiley | es_ES |
dc.relation.ispartof | Chem. Eur. J. | es_ES |
dc.rights | Atribución-NoComercial-SinDerivadas 3.0 España | * |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/3.0/es/ | * |
dc.subject | Chirality | es_ES |
dc.subject | Internal rotation | es_ES |
dc.subject | Microwave spectroscopy | es_ES |
dc.subject | Microwave three-wave mixing | es_ES |
dc.subject | Terpenes | es_ES |
dc.title | Structure Determination, Conformational Flexibility, Internal Dynamics, and Chiral Analysis of Pulegone and Its Complex with Water | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.type.version | info:eu-repo/semantics/acceptedVersion | es_ES |
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