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Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy
Authors:Rachel L Meyer  Samuel M Greer  Anastasia V Blake  Samantha K Cary  Alexander S Ditter  Scott R Daly  Feng Li  Stosh A Kozimor  Ellen M Matson  Veronika Mocko  Gerald T Seidler  Benjamin W Stein  Samuel D Weinstein
Institution:1. Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, 87545 USA

Department of Chemistry, University of Rochester, Rochester, NY, 14627 USA;2. Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, 87545 USA;3. Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, 87545 USA

Department of Chemistry, University of Iowa, Iowa City, IA, 52242 USA;4. Department of Chemistry, University of Iowa, Iowa City, IA, 52242 USA;5. Department of Chemistry, University of Rochester, Rochester, NY, 14627 USA;6. Department of Physics, University of Washington, Seattle, WA, 98195-1560 USA

Abstract: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.
Keywords:iron  mixed-valent compounds  polyoxometalates  vanadium  X-ray absorption spectroscopy
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