dc.creator | Gómez, Margarita | es |
dc.creator | Pastor Navarro, Antonio | es |
dc.creator | Álvarez González, Eleuterio | es |
dc.creator | Olloqui Sariego, José Luis | es |
dc.creator | Galindo del Pozo, Agustín | es |
dc.date.accessioned | 2019-01-17T13:13:41Z | |
dc.date.available | 2019-01-17T13:13:41Z | |
dc.date.issued | 2018 | |
dc.identifier.citation | Gómez, M., Pastor Navarro, A., Álvarez González, E., Olloqui Sariego, J.L. y Galindo del Pozo, A. (2018). Halide encapsulation by dicarboxylate oxido-vanadium cage complexes. Dalton Transactions, 47, 2183-2191. | |
dc.identifier.issn | 1477-9234 | es |
dc.identifier.uri | https://hdl.handle.net/11441/81687 | |
dc.description.abstract | Compounds [Bu4N]2[V8O16(oda)4⊂2Cl], 1, [Bu4N]2[V8O16(glut)4⊂2Cl], 2, and [Bu4N][V4O8(glut)2⊂F], 3, (oda
= oxydiacetate, O(CH2COO)2
2−; glut = glutarate, CH2(CH2COO)2
2−) were obtained by a stepwise reaction
of in situ prepared [Bu4N]VO3 with HCl (or HF for 3) and then with the dicarboxylic acid X(CH2COOH)2
(X = O and CH2), under appropriate reaction conditions. Multinuclear magnetic resonance (1
H, 13C{1
H},
35Cl, 19F and 51V), electrochemical studies, X-ray structural determinations (single crystal and powder),
thermogravimetric analyses (TGA) and Density Functional Theory (DFT) calculations were employed to
characterise these polyoxovanadate complexes 1–3. They included encapsulated halide anions, two
chloride ions in 1 and 2 and one fluoride ion in 3, where the shape and dimensions of the cage were
governed by the halide size. The stabilizing template effect of the chloride ion towards the bowl-shaped
[V4O8(OOCR)4] fragment (i.e. the half part of 1 and 2), containing a crown-shaped {V4O8} subunit, or that
of the fluoride ion towards the planar {V4O8} moiety in 3, was definitively demonstrated by DFT calculations. The HOMO composition of 1 prompted us to study the possible oxidation of the two encapsulated chloride ions toward a chlorine molecule. The electrochemical behaviors of 1–3 were thus investigated. However, the chlorine molecule in the model [V8O16(oda)4⊂(Cl2)], 6c, was not capable to stabilise
the polyoxovanadate cage [V8O16(oda)4], 4c, according to DFT calculations. | es |
dc.description.sponsorship | Junta de Andalucía (Proyecto de Excelencia FQM-7079) | es |
dc.description.sponsorship | Ministerio de Economía y Competitividad (CTQ2014-52641-P) | es |
dc.description.sponsorship | Universidad de Sevilla (VI Plan Propio) | es |
dc.format | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | The Royal Society of Chemistry | es |
dc.relation.ispartof | Dalton Transactions, 47, 2183-2191. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Halide encapsulation by dicarboxylate oxido-vanadium cage complexes | es |
dc.type | info:eu-repo/semantics/article | es |
dcterms.identifier | https://ror.org/03yxnpp24 | |
dc.type.version | info:eu-repo/semantics/acceptedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Inorgánica | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Física | es |
dc.relation.projectID | CTQ2014-52641-P | es |
dc.relation.projectID | FQM-7079 | es |
dc.relation.publisherversion | http://dx.doi.org/10.1039/c7dt04251e | es |
dc.identifier.doi | 10.1039/c7dt04251e | es |
idus.format.extent | 9 p. | es |
dc.journaltitle | Dalton Transactions | es |
dc.publication.volumen | 47 | es |
dc.publication.initialPage | 2183 | es |
dc.publication.endPage | 2191 | es |