Issue 47, 2013

Monolacunary Keggin polyoxometalates connected to ten 4d or 4f metal atoms

Abstract

The rational self-assembly of mono-lacunary Keggin clusters with 4d and 4f metal salts via a conventional method has yielded two novel polyoxometalate-based 4d–4f heterometallic compounds containing lacunary Keggin anions connected to ten metal atoms: {[Ag{Ag2(H2O)4}{Ln(H2O)6}2H ⊂ {SiW11Ln(H2O)4O39}2nH2O (Ln = Ce and n = 7 for 1, Ln = Pr and n = 3 for 2). Their structures were determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. A structural feature in 1 and 2 is that each [SiW11O39]8− cluster (SiW11) is connected to ten metals (five Ag+ and five Ln3+ cations), representing the highest number of connected metal atoms to any mono-lacunary Keggin anion to date. This large connectivity leads to a structure with a purely inorganic 3D framework with two kinds of channels along the [100] and [010] directions. The magnetic properties of both compounds show the expected magnetic moments (0.8 and 1.6 amu K mol−1 per Ce3+ and Pr3+ ion, respectively) and confirm the presence of isolated Ce3+ and Pr3+ ions.

Graphical abstract: Monolacunary Keggin polyoxometalates connected to ten 4d or 4f metal atoms

Supplementary files

Article information

Article type
Paper
Submitted
12 Jul 2013
Accepted
10 Sep 2013
First published
10 Sep 2013

Dalton Trans., 2013,42, 16596-16601

Monolacunary Keggin polyoxometalates connected to ten 4d or 4f metal atoms

H. Pang, C. J. Gómez-García, J. Peng, H. Ma, C. Zhang and Q. Wu, Dalton Trans., 2013, 42, 16596 DOI: 10.1039/C3DT51899J

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