Incipient class II mixed valency in a plutonium solid-state compound

Samantha K. Cary; Shane S. Galley; Matthew L. Marsh; David L. Hobart; Ryan E. Baumbach; Justin N. Cross; Jared T. Stritzinger; Matthew J. Polinski; Laurent Maron; Thomas E. Albrecht-Schmitt

doi:10.1038/nchem.2777

Incipient class II mixed valency in a plutonium solid-state compound

Samantha K. Cary, Shane S. Galley, Matthew L. Marsh, David L. Hobart, Ryan E. Baumbach, Justin N. Cross, Jared T. Stritzinger, Matthew J. Polinski, Laurent Maron, Thomas E. Albrecht-Schmitt

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

26 Scopus citations

Abstract

Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent Pu^III/Pu^IV solid-state compound, Pu₃(DPA)₅(H₂O)₂ (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [Pu^III(DPA)(H₂O)₄] Br and Pu^IV(DPA)₂(H₂O)₃·3H₂O, as well as by a second mixed-valent compound, Pu^III[Pu^IV(DPA)₃H_0.5]₂, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu₃(DPA)₅(H₂O)₂ and in the IVCT.

Original language	English
Pages (from-to)	856-861
Number of pages	6
Journal	Nature Chemistry
Volume	9
Issue number	9
DOIs	https://doi.org/10.1038/nchem.2777
State	Published - Sep 1 2017
Externally published	Yes

Funding

This material is based upon work supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program under award number DE-FG02-13ER16414.We are especially grateful for the assistance and supervision by the Office of Environmental Health and Safety at Florida State University, specifically J. A. Johnson and A. L. Gray of the Office of Radiation Safety for their facilitation of these studies. Magnetization measurements using the VSM SQUID MPMS were performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative agreement number DMR-1157490, the State of Florida, and the US Department of Energy. We are grateful for helpful discussions with N. M. Edelstein, M. P. Jensen and G. Liu.

Funders	Funder number
Heavy Elements Chemistry Program	DE-FG02-13ER16414
Office of Basic Energy Sciences
Office of Environmental Health and Safety at Florida State University
State of Florida
US Department of Energy
National Science Foundation	DMR-1157490
Office of Science

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title = "Incipient class II mixed valency in a plutonium solid-state compound",

abstract = "Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent PuIII/PuIV solid-state compound, Pu3(DPA)5(H2O)2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [PuIII(DPA)(H2O)4] Br and PuIV(DPA)2(H2O)3·3H2O, as well as by a second mixed-valent compound, PuIII[PuIV(DPA)3H0.5]2, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu3(DPA)5(H2O)2 and in the IVCT.",

author = "Cary, {Samantha K.} and Galley, {Shane S.} and Marsh, {Matthew L.} and Hobart, {David L.} and Baumbach, {Ryan E.} and Cross, {Justin N.} and Stritzinger, {Jared T.} and Polinski, {Matthew J.} and Laurent Maron and Albrecht-Schmitt, {Thomas E.}",

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AU - Cary, Samantha K.

AU - Galley, Shane S.

AU - Marsh, Matthew L.

AU - Hobart, David L.

AU - Baumbach, Ryan E.

AU - Cross, Justin N.

AU - Stritzinger, Jared T.

AU - Polinski, Matthew J.

AU - Maron, Laurent

AU - Albrecht-Schmitt, Thomas E.

PY - 2017/9/1

Y1 - 2017/9/1

N2 - Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent PuIII/PuIV solid-state compound, Pu3(DPA)5(H2O)2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [PuIII(DPA)(H2O)4] Br and PuIV(DPA)2(H2O)3·3H2O, as well as by a second mixed-valent compound, PuIII[PuIV(DPA)3H0.5]2, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu3(DPA)5(H2O)2 and in the IVCT.

AB - Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin-Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent PuIII/PuIV solid-state compound, Pu3(DPA)5(H2O)2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [PuIII(DPA)(H2O)4] Br and PuIV(DPA)2(H2O)3·3H2O, as well as by a second mixed-valent compound, PuIII[PuIV(DPA)3H0.5]2, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu3(DPA)5(H2O)2 and in the IVCT.

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Incipient class II mixed valency in a plutonium solid-state compound

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