X-ray and nuclear spectroscopies to reveal the element specific oxidation states and electronic spin states for nanoparticulated manganese cyanidoferrates and analogs

利用X射线和核光谱技术揭示纳米颗粒锰氰铁酸盐及其类似物的元素特定氧化态和电子自旋态

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Abstract

In this publication, the potential non-gadolinium magnetic resonant imaging agent - the nanoparticulate K(2)Mn[Fe(CN)(6)], its comparison sample KFe[Co(CN)(6)], as well as their reference samples were measured and analyzed with Mn, Co and Fe L-edge X-ray absorption spectroscopy (L XAS). From the information obtained, we conclude that K(2)Mn[Fe (CN)(6)] has a high spin (hs)-Mn(II) and a low spin (ls)-Fe(II), while KFe[Co(CN)(6)] has a hs-Fe(II) and a ls-Co(III). In these Prussian blue (PB) analog structures, L XAS also concluded that the hs-Mn(II) in K(2)Mn[Fe(CN)(6)] or the hs-Fe(II) in KFe[Co(CN)(6)] is bonding to the N in the [M(CN)(6)](4-/3-) ions [where M = Fe(II) or Co(III)], while the ls-Fe(II) in K(2)Mn[Fe(CN)(6)] or the ls-Co(III) in KFe[Co(CN)(6)] is bonding to the C in the [M(CN)(6)](4-/3-) ion, suggesting the complexed metalloligand [Mn(II) or Fe(II)] occupy the N-bound site in PB. Then, nuclear resonant vibrational spectroscopy (NRVS) was used to confirm the results from the L XAS measurements: the Mn(II), Eu(III), Gd(III), Fe(II) cations complexed by [M(CN)(6)](n-)-metalloligand are all taking the N-bound site in the PB-like structures. Our NRVS studies also approve that iron in K(2)Mn[Fe(CN)(6)] compound has 2+ oxidation state and is surrounding by the C donor atoms in the [M(CN)(6)](n-) ions.

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