Interplay between transition-metal K-edge XMCD, slight structural distortions and magnetism in a series of trimetallic (CoxNi(1-x))4[Fe(CN)6]3/8 Prussian blue analogues.

The magnetic properties of a series of trimetallic (Co,Ni)Fe Prussian blue analogues (PBAs) were investigated by SQUID magnetometry and X-ray magnetic circular dichroism (XMCD) at the three transition metal (TM) K-edges. In turn, the PBA trimetallic series was used as a tool in order to better understand the information contained in TM K-edge XMCD and particularly the chemical nature of the probed species (extended sub-lattice or localized entities). The results show that the magnetic behavior of the compounds is dictated by competing exchange interactions between the Co-Fe and Ni-Fe pairs, without spin frustration. They also show that XMCD at the TM K-edge is a local atomic probe of the element at the N side of the cyanide bridge and a local probe of the absorbing atom and its first magnetic neighbors on the C side of the bridge. At last, XMCD at the TM K-edge turns out to be highly sensitive to very small structural distortions.

Interplay between Transition-Metal K-edge XMCD and Magnetism in Prussian Blue Analogs.

To disentangle the information contained in transition-metal K-edge X-ray magnetic circular dichroism (XMCD), two series of Prussian blue analogs (PBAs) were investigated as model compounds. The number of 3d electrons and the magnetic orbitals have been varied on both sites of the bimetallic cyanide polymer by combining with the hexacyanoferrate or the hexacyanochromate entities' various divalent metal ions A2+ (Mn2+, Fe2+, Co2+, Ni2+, and Cu2+). These PBA were studied by Fe and Cr X-ray absorption spectroscopy and XMCD. The results, compared to those obtained at the A K-edges in a previous work, show that transition-metal K-edge XMCD is very sensitive to orbital symmetry and can therefore give valuable information on the local structure of the magnetic centers. Expressions of the intensity of the main 1s → 4p contribution to the signal are proposed for all K-edges and all compounds. The results pave the way toward a new tool for molecular materials able to give access to valuable information on the local orientation of the magnetic moments or to better understand the role of 4p orbitals involved in their magnetic properties.

Toward Quantitative Magnetic Information from Transition Metal K-Edge XMCD of Prussian Blue Analogs.

Two series of Prussian blue analogs (PBA) were used as model compounds in order to disentangle the information contained in X-ray magnetic circular dichroism (XMCD) at the K-edges of transition metals. The number of 3d electrons on one site of the bimetallic cyanide polymer has been varied by associating to the [Fe(CN)6]3- or the [Cr(CN)6]3- precursors various divalent metal ions A2+ (Mn2+, Fe2+, Co2+, Ni2+, and Cu2+). The compounds were studied by X-ray diffraction and SQUID magnetometry, as well as by X-ray absorption spectroscopy and XMCD at the K-edges of the A2+ transition metal ion. The study shows that the 1s → 4p contribution to the A K-edge XMCD signal can be related to the electronic structure and the magnetic behavior of the probed A2+ ion: the shape of the signal to the filling of the 3d orbitals, the sign of the signal to the direction of the magnetic moment with respect to the applied magnetic field, the intensity of the signal to the total spin number SA, and the area under curve to the Curie constant CA. The whole study hence demonstrates that PBAs are particularly well-adapted for understanding the information contained in the transition metals K-edge XMCD signals. It also offers new perspectives toward the full disentangling of the information contained in these signals and access to new insights into materials magnetic properties.

A cookbook for the investigation of coordination polymers by transition metal K-edge XMCD.

In order to disentangle the physical effects at the origin of transition metal K-edge X-ray magnetic circular dichroism (XMCD) in coordination polymers and quantify small structural distortions from the intensity of these signals, a systematic investigation of Prussian blue analogs as model compounds is being conducted. Here the effects of the temperature and of the external magnetic field are tackled; none of these external parameters modify the shape of the XMCD signal but they both critically modify its intensity. The optimized experimental conditions, as well as a reliable and robust normalization procedure, could thus be determined for the study of the intrinsic parameters. Through an extended discussion on measurements on other XMCD-dedicated beamlines and for other coordination compounds, we finally provide new transition metal K-edge XMCD users with useful information to initiate and successfully carry out their projects.