Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type \(M)M-5\(12)Fe-30(III) (M = Mo-VI, W-VI)

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.
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Dalton Transactions, Royal Society of Chemistry, 2013, 42 (22), pp.7924-7935. 〈10.1039/c3dt32759k〉
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Soumis le : mardi 2 mai 2017 - 16:05:09
Dernière modification le : vendredi 19 octobre 2018 - 11:46:41

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Karsten Kuepper, Christine Derks, Christian Taubitz, Manuel Prinz, Loic Joly, et al.. Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type \(M)M-5\(12)Fe-30(III) (M = Mo-VI, W-VI). Dalton Transactions, Royal Society of Chemistry, 2013, 42 (22), pp.7924-7935. 〈10.1039/c3dt32759k〉. 〈hal-01517067〉

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