Logo image
Back
Alkali Counterion-Dependent Crystallization of Uranium(IV)-Chloro Structural Units
Journal article   Open access   Peer reviewed

Alkali Counterion-Dependent Crystallization of Uranium(IV)-Chloro Structural Units

Madeline C Shore, Jennifer N Wacker, Pere Miró, Jeffery A Bertke and Karah E Knope
Inorganic chemistry, Vol.64(29), pp.14799-14809
07/28/2025
DOI: 10.1021/acs.inorgchem.5c00822
PMCID: PMC12308800
PMID: 40506416
url
https://doi.org/10.1021/acs.inorgchem.5c00822View
Published (Version of record) Open Access

Related content

Is publication of

Is publication of

Is publication of

Is publication of

Abstract

The synthesis, structural characterization, and spectroscopic properties of five tetravalent uranium (U) phases including Li6[U4(μ3-O)2Cl18(H2O)2]·10H2O (1), [U(H2O)4Cl4] (2), [U(H2O)4Cl4]·KCl (3), Rb2UCl6 (4), and Cs2UCl6 (5) are reported. Notably, a change in the U4+ solid-state structural unit was observed based on the identity of the alkali counterion used in the synthesis. Li1+ yielded a tetranuclear oxo-bridged cluster, [U4(μ3-O)2Cl18(H2O)2]6–, Na1+ and K1+ yielded two structurally distinct [U(H2O)4Cl4] complexes, and Rb1+ and Cs1+ resulted in [UCl6]2– as the dominant phases. The spectroscopic properties of the compounds were analyzed using Raman and UV–vis–NIR absorption spectroscopy. The UV–vis–NIR spectra of compounds 1–5 exhibited transitions consistent with uranium in the +4 oxidation state. Clear differences in the absorption band splitting were observed and are likely attributed to differences in metal ion coordination, crystal field effects, and outer sphere interactions Overall, this work demonstrates the utility of noncovalent interactions in tuning the crystallization of various metal complexes from otherwise identical reaction solutions and provides further evidence that counterions impact the composition and structure of actinide complexes isolated in the solid state. In this way, this work affords important insight into directing and controlling the structure of actinide complexes and clusters.

Details

Metrics

8 Record Views
2 Times Cited - Web of Science
Logo image