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A number of technologies would benefit from developing inorganic compounds and materials with specific electronic and magnetic exchange properties. Unfortunately, designing compounds with these properties is difficult because metal⋅⋅⋅metal coupling schemes are hard to predict and control. Fully characterizing communication between metals in existing compounds that exhibit interesting properties could provide valuable insight and advance those predictive capabilities. One such class of molecules are the series of Lindqvist iron-functionalized and hexavanadium polyoxovanadate-alkoxide clusters, which we characterized here using V K-edge X-ray absorption spectroscopy. Substantial changes in the pre-edge peak intensities were observed that tracked with the V 3d-electron count. The data also suggested substantial delocalization between the vanadium cations. Meanwhile, the FeIII cations were electronically isolated from the polyoxovanadate core.

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear-fuel cycles. Herein, we describe the preparation of (NBu4)Am[S2P(tBu2C12H6)]4and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., NdIII) and an isoelectronic one (EuIII). The results include the first measurement of an Am−S bond length, with a mean value of 2.921(9) Å, by single-crystal X-ray diffraction. Comparison with the EuIIIand NdIIIcomplexes revealed subtle electronic differences between the complexes of AmIIIand the lanthanides.