Multi-edge X-ray absorption spectroscopy of thorium, neptunium and plutonium hexacyanoferrate compounds

Although transition metal cyano bimetallic compounds have been well known for decades for their interesting optical and magnetic properties, reports on actinide hexacyanoferrate compounds are scarce. For instance, a thorough structural description is still lacking. Another question is the possible covalency or charge transfer effects in these materials that are known to foster electron delocalization with a large variety of transition metal cations. In this paper, new members of the actinide(IV) hexacyanoferrates have been synthesized with Th, Np and Pu. This is the first review of thorium to plutonium hexacyanoferrate compounds since the early investigations during the Manhattan Project some 70 years ago. We have carried out an extensive structural characterization using powder X-ray Diffraction (XRD), X-ray Absorption Spectroscopy (XAS) and X-ray microscopy for the plutonium adduct. The crystallographic space group of microcrystalline Th, Np and Pu hexacyanoferrate compounds appears to be very similar to that of the early lanthanide adducts, suggesting that the tetravalent actinides are arranged in a tricapped trigonal prismatic polyhedron of coordination number 9, in which the actinide atom is bonded to six nitrogen atoms and to three water molecules. Further combined analysis of the iron K-edge and actinide L-III-edge EXAFS data and XRD data provided the basis for a three-dimensional molecular model. Structural data in terms of actinide-ligand bond lengths have been compared to those reported for the parent lanthanide(III) compounds, confirming the structural similarities. In addition, two new structures with the thorium cation have been obtained and described using single-crystal XRD: (H5O2)[Th(DMF)(5)(H2O)](2)[Fe(CN)(6)](3) and [Th(DMF)(4)(H2O)(3)][Fe(CN)(6)](NO3)center dot 2H(2)O. This structural description of the Th, Np and Pu hexacyanoferrate system will be followed by a semi-quantitative electronic description of the actinide-cyano bond using NEXAFS data analysis in a coming paper.