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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https://osnadocs.ub.uni-osnabrueck.de/handle/urn:nbn:de:gbv:700-2013082611480
https://osnadocs.ub.uni-osnabrueck.de/handle/urn:nbn:de:gbv:700-2013082611480
| 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://osnadocs.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: | FB06 - Hochschulschriften |
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|---|---|---|---|---|
| c3dt32759k.pdf | Artikel | 5,84 MB | Adobe PDF | c3dt32759k.pdf  View/Open |
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