Journal article
Solid state 59Co NMR study of a np(VII) compound
Inorganica Chimica Acta, Vol.600, 123259
09/24/2026
DOI: 10.1016/j.ica.2026.123259
Abstract
Np(VII) compounds with [Co(NH3)6]3+ cations were synthesized and structurally examined using powder X-ray diffraction. Multiple phases were observed, consisting of octahedral [Co(NH3)6]3+ cations, discrete tetragonal bipyramidal [NpO4(OH)2]3− anions, and waters of hydration. Electric field gradient tensors at Co sites were measured by solid state 59Co nuclear magnetic resonance (NMR) spectroscopy and compared with theoretical calculations. The relative contributions of the chemical shift and electric field tensors to the NMR lineshape were determined by recording spectra at field strengths of 7.04 and 11.74 Tesla. Further, the evolution of structure and morphology as a function of sample age and the effects on NMR spectral parameters has also been investigated. These results demonstrate the use of NMR at multiple fields to expand understanding of the stability and electronic structure of high valent neptunium compounds.
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•Np(VII) exemplifies the highest oxidation state accessible to f-block elements.•Heptavalent Np incorporates in hydrates of the form [Co(NH3)6]y[NpO4(OH)2]y∙xH2O.•Two distinct crystalline phases are produced in approximately equal amounts.•Structure, morphology, and oxidation states evolve over a 460 d time scale.
Details
- Title: Subtitle
- Solid state 59Co NMR study of a np(VII) compound
- Creators
- Khyati Anand - Pacific Northwest National LaboratoryKhusboo Rana - Pacific Northwest National LaboratorySejun Park - Pacific Northwest National LaboratorySergey Sinkov - Pacific Northwest National LaboratoryGrant C. Benthin - University of IowaHarindu Rajapaksha - University of IowaEmma L. Markun - University of IowaShalini Tripathi - Pacific Northwest National LaboratorySoumya R. Dash - University at Buffalo, State University of New YorkEdgar C. Buck - Pacific Northwest National LaboratoryJochen Autschbach - University at Buffalo, State University of New YorkHerman Cho - Pacific Northwest National LaboratoryTori Z. Forbes - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Inorganica Chimica Acta, Vol.600, 123259
- DOI
- 10.1016/j.ica.2026.123259
- ISSN
- 0020-1693
- eISSN
- 1873-3255
- Publisher
- Elsevier B.V
- Grant note
- Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Heavy Element Chemistry Program: FWP 73200 U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program: DE-SC0001136
Synthesis and characterization of the Np (VII) compound and efforts of GHB, HR, ELM, and TZF were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry program under Award Number DE-SC0023995. Work at PNNL (PXRD data analysis, NMR sample preparation, and spectroscopy) was supported by the U.S. Department of Energy, Office ofScience, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Heavy Element Chemistry Program (FWP 73200) . JA acknowledges financial support for the DFT NMR calculations from the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program, under grant DE-SC0001136.
- Language
- English
- Electronic publication date
- 05/05/2026
- Date published
- 09/24/2026
- Academic Unit
- Civil and Environmental Engineering; Core Research Facilities; Chemistry
- Record Identifier
- 9985161449902771
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