Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy

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

doi:10.1002/chem.202003625

Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy

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

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

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 Fe^III cations were electronically isolated from the polyoxovanadate core.

Original language	English
Pages (from-to)	1592-1597
Number of pages	6
Journal	Chemistry - A European Journal
Volume	27
Issue number	5
DOIs	https://doi.org/10.1002/chem.202003625
State	Published - Jan 21 2021
Externally published	Yes

Funding

This work was primarily funded by the Heavy Element Chemistry Program Basic Energy Sciences Office of Basic Energy Sciences, U.S. Department of Energy (DOE). Los Alamos National Laboratory (LANL) is an affirmative action/equal opportunity employer, managed by Triad National Security, LLC, for the NNSA of the U.S. DOE (contract 89233218CNA000001). The DOE Office of Science Graduate Student Research Fellowship (SCGSR) Program supported R. L. M. and A. V. B., S.G.M. was supported be the LANL Directors Fellowship Program, and S. K. C. was supported by the LANL Hoffman Distinguished Postdoctoral Fellowship. R. L. M., F. L., S. D. W., and E. M. M. acknowledge the National Science Foundation (CHE-1653195). S. R. D. acknowledges the U.S. DOE, Office of Science, Office of Basic Energy Sciences, Separation Science program (DE-SC0019426). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U. S. DOE, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515. This work was primarily funded by the Heavy Element Chemistry Program Basic Energy Sciences Office of Basic Energy Sciences, U.S. Department of Energy (DOE). Los Alamos National Laboratory (LANL) is an affirmative action/equal opportunity employer, managed by Triad National Security, LLC, for the NNSA of the U.S. DOE (contract 89233218CNA000001). The DOE Office of Science Graduate Student Research Fellowship (SCGSR) Program supported R. L. M. and A. V. B., S.G.M. was supported be the LANL Directors Fellowship Program, and S. K. C. was supported by the LANL Hoffman Distinguished Postdoctoral Fellowship. R. L. M., F. L., S. D. W., and E. M. M. acknowledge the National Science Foundation (CHE‐1653195). S. R. D. acknowledges the U.S. DOE, Office of Science, Office of Basic Energy Sciences, Separation Science program (DE‐SC0019426). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U. S. DOE, Office of Science, Office of Basic Energy Sciences under Contract No. DE‐AC02‐76SF00515.

Funders	Funder number
LANL Hoffman Distinguished Postdoctoral Fellowship
Office of Basic Energy Sciences
Separation Science program	DE‐SC0019426
U. S. DOE	DE‐AC02‐76SF00515
U.S. DOE
National Science Foundation	CHE‐1653195
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Los Alamos National Laboratory	89233218CNA000001

Keywords

X-ray absorption spectroscopy
iron
mixed-valent compounds
polyoxometalates
vanadium

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10.1002/chem.202003625

Cite this

Meyer, R. L., Greer, S. M., Blake, A. V., Cary, S. K., Ditter, A. S., Daly, S. R., Li, F., Kozimor, S. A., Matson, E. M., Mocko, V., Seidler, G. T., Stein, B. W., & Weinstein, S. D. (2021). Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy. Chemistry - A European Journal, 27(5), 1592-1597. https://doi.org/10.1002/chem.202003625

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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.",

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AU - Cary, Samantha K.

AU - Ditter, Alexander S.

AU - Daly, Scott R.

AU - Li, Feng

AU - Kozimor, Stosh A.

AU - Matson, Ellen M.

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AU - Seidler, Gerald T.

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AB - 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.

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Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy

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