Issue 4, 2014

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

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

Supplementary files

Article information

Article type
Paper
Submitted
19 Jul 2013
Accepted
05 Nov 2013
First published
05 Nov 2013

Dalton Trans., 2014,43, 1906-1916

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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements