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Issue 4, 2014
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Syntheses, structures, properties and DFT study of hybrid inorganic–organic architectures constructed from trinuclear lanthanide frameworks and Keggin-type polyoxometalates

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Abstract

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.

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

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Article information


Submitted
19 Jul 2013
Accepted
05 Nov 2013
First published
05 Nov 2013

Dalton Trans., 2014,43, 1906-1916
Article type
Paper

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

M. Mirzaei, H. Eshtiagh-Hosseini, N. Lotfian, A. Salimi, A. Bauzá, R. Van Deun, R. Decadt, M. Barceló-Oliver and A. Frontera, Dalton Trans., 2014, 43, 1906
DOI: 10.1039/C3DT51971F

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