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)

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Title: 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)
Authors: Kuepper, Karsten
Derks, Christine
Taubitz, Christian
Prinz, Manuel
Joly, Loic
Kappler, Jean-Paul
Postnikov, Andrei
Yang, Wanli
Kuznetsova, Tatyana V.
Wiedwald, Ulf
Ziemann, Paul
Neumann, Manfred
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.
Citations: Dalton Transactions 42(22): 7924–7935 (2013)
URL: https://repositorium.ub.uni-osnabrueck.de/handle/urn:nbn:de:gbv:700-2013082611480
Subject Keywords: Giant Keplerate-type molecules; X-ray absorption spectroscopy
Issue Date: 26-Aug-2013
License name: Namensnennung-NichtKommerziell-KeineBearbeitung 3.0 Unported
License url: http://creativecommons.org/licenses/by-nc-nd/3.0/
Type of publication: Einzelbeitrag in einer wissenschaftlichen Zeitschrift [article]
Appears in Collections:FB04 - Hochschulschriften

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