Issue 22, 2013

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

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)

Article information

Article type
Paper
Submitted
19 Nov 2012
Accepted
22 Jan 2013
First published
23 Jan 2013
This article is Open Access
Creative Commons BY license

Dalton Trans., 2013,42, 7924-7935

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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