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)

Kuepper K, Derks C, Taubitz C, Prinz M, Joly L, Kappler J-P, Postnikov A, Yang W, Kuznetsova TV, Wiedwald U, Ziemann P, et al. (2013)
Dalton Transactions 42(22): 7924-7935.

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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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Kuepper K, Derks C, Taubitz C, 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. 2013;42(22):7924-7935.
Kuepper, K., Derks, C., Taubitz, C., Prinz, M., Joly, L., Kappler, J. - P., Postnikov, A., et al. (2013). 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, 42(22), 7924-7935.
Kuepper, K., Derks, C., Taubitz, C., Prinz, M., Joly, L., Kappler, J. - P., Postnikov, A., Yang, W., Kuznetsova, T. V., Wiedwald, U., et al. (2013). 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 42, 7924-7935.
Kuepper, K., et al., 2013. 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, 42(22), p 7924-7935.
K. Kuepper, 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, vol. 42, 2013, pp. 7924-7935.
Kuepper, K., Derks, C., Taubitz, C., Prinz, M., Joly, L., Kappler, J.-P., Postnikov, A., Yang, W., Kuznetsova, T.V., Wiedwald, U., Ziemann, P., Neumann, M.: 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. 42, 7924-7935 (2013).
Kuepper, Karsten, Derks, Christine, Taubitz, Christian, Prinz, Manuel, Joly, Loic, Kappler, Jean-Paul, Postnikov, Andrej, Yang, Wanli, Kuznetsova, Tatyana V., Wiedwald, Ulf, Ziemann, Paul, and Neumann, Manfred. “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 42.22 (2013): 7924-7935.
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