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Issue 22, 2013
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Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12FeIII30 (M = MoVI, WVI)

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Abstract

Giant Keplerate-type molecules with a {Mo72Fe30} core show a number of very interesting properties, making them particularly promising for various applications. So far, only limited data on the electronic structure of these molecules from X-ray spectra and electronic structure calculations have been available. Here we present a combined electronic and magnetic structure study of three Keplerate-type nanospheres—two with a {Mo72Fe30} core and one with a {W72Fe30} core by means of X-ray absorption spectroscopy, X-ray magnetic circular dichroism (XMCD), SQUID magnetometry, and complementary theoretical approaches. Furthermore, we present detailed studies of the Fe3+-to-Fe2+ photoreduction process, which is induced under soft X-ray radiation in these molecules. We observe that the photoreduction rate greatly depends on the ligand structure surrounding the Fe ions, with negatively charged ligands leading to a dramatically reduced photoreduction rate. This opens the possibility of tailoring such polyoxometalates by X-ray spectroscopic studies and also for potential applications in the field of X-ray induced photochemistry.

Graphical abstract: Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12FeIII30 (M = MoVI, WVI)

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Publication details

The article was received on 19 Nov 2012, accepted on 22 Jan 2013 and first published on 23 Jan 2013


Article type: Paper
DOI: 10.1039/C3DT32759K
Dalton Trans., 2013,42, 7924-7935
  • Open access: Creative Commons BY license
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    Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M5}12FeIII30 (M = MoVI, WVI)

    K. Kuepper, C. Derks, C. Taubitz, M. Prinz, L. Joly, J. Kappler, A. Postnikov, W. Yang, T. V. Kuznetsova, U. Wiedwald, P. Ziemann and M. Neumann, Dalton Trans., 2013, 42, 7924
    DOI: 10.1039/C3DT32759K

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