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Issue 38, 2008
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Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy

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Abstract

A series of thin films of Prussian blue analogues is investigated by X-ray absorption spectroscopy (XAS) at the Fe, Co and Mn L2,3-edges. The ligand field multiplet theory enables us to examine accurately the electronic structure of these materials. Experimental XAS spectra of CoFe Prussian blue analogues are successfully reproduced using a ground state configuration including metal-to-ligand (MLCT) and ligand-to-metal charge transfer (LMCT) at the Co and Fe L2,3-edges. In particular, a huge improvement is achieved for satellite peaks at the Co(III) L2,3-edges compared to previous calculations in the literature based on LMCT effects only. On the other hand, XAS spectra of MnFe analogues synthesized for the first time, can be reproduced conveniently by taking into account either MLCT or LMCT depending on the conditions of the sample preparation. For each thin film, the proportion of the different oxidation states of Co, Fe and Mn is evaluated. Unexpectedly, this analysis reveals the presence of a significant amount of a reduced phase, which turns out to be strongly dependent on the sample synthesis and storage conditions.

Graphical abstract: Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy

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Article information


Submitted
22 Apr 2008
Accepted
20 Jun 2008
First published
06 Aug 2008

Phys. Chem. Chem. Phys., 2008,10, 5882-5889
Article type
Paper

Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy

S. Bonhommeau, N. Pontius, S. Cobo, L. Salmon, F. M. F. de Groot, G. Molnár, A. Bousseksou, H. A. Dürr and W. Eberhardt, Phys. Chem. Chem. Phys., 2008, 10, 5882
DOI: 10.1039/B806783J

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