Syntheses, structures, properties and DFT study of hybrid inorganic¿organic architectures constructed from trinuclear lanthanide frameworks and Keggin-type polyoxometalates

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dc.contributor.author Mirzaei, Masoud
dc.contributor.author Eshtiagh Hosseini, Hossein
dc.contributor.author Lotfian, Nahid
dc.contributor.author Salimi, Alireza
dc.contributor.author Bauzá Riera, Antonio
dc.contributor.author Van Deun, Rik
dc.contributor.author Decadt, Roel
dc.contributor.author Barcelo-Oliver, Miquel
dc.contributor.author Frontera Beccaria, Antonio
dc.date.accessioned 2018-09-24T10:16:07Z
dc.identifier.uri http://hdl.handle.net/11201/147615
dc.description.abstract [eng] In this paper we report the synthesis and X-ray characterization of four novel hybrid inorganic-organic assemblies generated from H4SiW12O40 as Keggin-type polyoxometalates (POM) and, in three of them, a trinuclear lanthanide cluster of type {Na(H2O)3[Ln(HCAM)(H2O)3]3}4+ is formed, where Ln metal is La in compound 1, Ce in compound 2, and Eu in compound 3 (H3CAM = chelidamic acid or 2,6-dicarboxy-4- hydroxypyridine). These compounds represent the first POM-based inorganic-organic assemblies using chelidamic acid as an organic ligand. The thermal stability of the organic ligand is crucial, since pyridine- 2,6-bis(monothiocarboxylate) instead of chelidamic acid is used (compound 4) under the same synthesis conditions, the decomposition of the ligand to pyridine was observed leading to the formation of colorless crystals of a pseudo hybrid inorganic-organic assembly. In compound 4 the hybrid inorganic-organic assembly is not formed and the organic part simply consists of four molecules of protonated pyridine acting as counterions of the [SiW12O40]4- counterpart. The luminescent properties of compounds 1 and 3 have been investigated and their solid state architectures have been analyzed. Whereas compound 1 only shows ligand emission, the Eu3+ emission in compound 3 is discussed in detail. We have found that unprecedented anion-π interactions between the POM, which is a tetra-anion, and the aromatic rings play a crucial role in the crystal packing formation. To the best of our knowledge, this is the first report that describes and analyzes this interaction in Keggin-type POM based inorganic-organic frameworks. The energetic features of these interactions in the solid state have been analyzed using DFT calculations in some model systems predicted by us.
dc.format application/pdf
dc.relation.isformatof Versió postprint del document publicat a: https://doi.org/10.1039/C3DT51971F
dc.relation.ispartof Dalton Transactions, 2014, vol. 43, num. 4, p. 1906-1916
dc.rights (c) Mirzaei, Masoud et al., 2014
dc.subject.classification 54 - Química
dc.subject.other 54 - Chemistry. Crystallography. Mineralogy
dc.title Syntheses, structures, properties and DFT study of hybrid inorganic¿organic architectures constructed from trinuclear lanthanide frameworks and Keggin-type polyoxometalates
dc.type info:eu-repo/semantics/article
dc.type info:eu-repo/semantics/acceptedVersion
dc.date.updated 2018-09-24T10:16:07Z
dc.date.embargoEndDate info:eu-repo/date/embargoEnd/2075-01-01
dc.embargo 2075-01-01
dc.rights.accessRights info:eu-repo/semantics/embargoedAccess
dc.identifier.doi https://doi.org/10.1039/C3DT51971F


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