Synthesis, Structural, and Electronic Properties of K4PuVIO2(CO3)3(cr): An Environmentally Relevant Plutonium Carbonate Complex

Ivan Pidchenko; Juliane März; Myrtille O J Y Hunault; Stephen Bauters; Sergei M Butorin; Kristina O Kvashnina

doi:10.1021/acs.inorgchem.0c01335

Synthesis, Structural, and Electronic Properties of K₄Pu^VIO₂(CO₃)_3(cr): An Environmentally Relevant Plutonium Carbonate Complex

Inorg Chem. 2020 Sep 8;59(17):11889-11893. doi: 10.1021/acs.inorgchem.0c01335. Epub 2020 Aug 26.

Authors

Ivan Pidchenko^{1

2}, Juliane März², Myrtille O J Y Hunault³, Stephen Bauters^{1

2}, Sergei M Butorin⁴, Kristina O Kvashnina^{1

2}

Affiliations

¹ Rossendorf Beamline at ESRF-The European Synchrotron, CS40220, 38043 Grenoble, Cedex 9, France.
² Institute of Resource Ecology, Helmholtz-Zentrum Dresden-Rossendorf, P.O. Box 510119, 01314 Dresden, Germany.
³ Synchrotron SOLEIL, L'Orme des Merisiers, Saint Aubin BP 48, 91192 Gif-sur-Yvette, France.
⁴ Molecular and Condensed Matter Physics, Department of Physics and Astronomy, Uppsala University, P.O. Box 516, 75236 Uppsala, Sweden.

PMID: 32846087
DOI: 10.1021/acs.inorgchem.0c01335

Abstract

The chemical properties of actinide materials are often predefined and described based on the data available for isostructural species. This is the case for potassium plutonyl (Pu^VI) carbonate, K₄Pu^VIO₂(CO₃)_3(cr), a complex relevant for nuclear technology and the environment, of which the crystallographic and thermodynamic properties of which are still lacking. We report here the synthesis and characterization of Pu^VI achieved by single-crystal X-ray diffraction analysis and high-energy-resolution fluorescence-detected X-ray absorption near-edge structure at the Pu M₄-edge coupled with electronic structure calculations. The crystallographic properties of Pu^VI are compared with isostructural uranium (U) and neptunium (Np) compounds. Actinyl (An^VI) axial bond lengths, [O-An^VI-O]²⁺, are correlated between solid, K₄An^VIO₂(CO₃)_3(cr), and aqueous, [An^VIO₂(CO₃)₃]^4-_(aq) species for the U^VI-Np^VI-Pu^VI series. The spectroscopic data are compared to KPu^VO₂CO_3(cr) and Pu^IVO_2(cr) to tackle the trend in the electronic structure of Pu^VI regarding the oxidation state changes and local structural modifications around the Pu atom.