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Synthesis, Characterization, and Density Functional Theory Investigation of the Solid-State [UO 2 Cl 4 (H 2 O)] 2– Complex
Journal article   Open access   Peer reviewed

Synthesis, Characterization, and Density Functional Theory Investigation of the Solid-State [UO 2 Cl 4 (H 2 O)] 2– Complex

Harindu Rajapaksha, Sara E. Mason and Tori Z. Forbes
Inorganic chemistry, Vol.62(35), pp.14318-14325
08/23/2023
DOI: 10.1021/acs.inorgchem.3c01725
PMCID: PMC10481372
PMID: 37610833
Appears in  UI Libraries Support Open Access
url
https://doi.org/10.1021/acs.inorgchem.3c01725View
Published (Version of record) Open Access

Abstract

A significant number of solid-state [UO2Cl4]2– coordination compounds have been synthesized and structurally characterized. Yet, despite their purposive relative abundance in aqueous solutions, characterization of aquachlorouranium(VI) complexes remain rare. In the current study, a solid-state uranyl aqua chloro complex ((C4H12N2)2[UO2Cl4(H2O)]Cl2) was synthesized using piperazinium as a charge-balancing ligand, and the structure was determined using single-crystal X-ray diffraction. Using periodic density functional theory, the electronic structure of the [UO2Cl4(H2O)]2– complex was compared to [UO2Cl4]2– to uncover the strengthening of the U═O bond in [UO2Cl4(H2O)]2–. Changes in the strength of the U═O bond were validated further with Raman and IR spectroscopy, where uranyl symmetrical (ν1) and asymmetrical (ν3) stretches were blue-shifted compared to the reference [UO2Cl4]2– complex. Furthermore, the formation energy of the solid-state (C4H12N2)2[UO2Cl4(H2O)]Cl2 complex was calculated to be −287.60 ± 1.75 kJ mol–1 using isothermal acid calorimetry. The demonstrated higher stability relative to the related [UO2Cl4]2– complex was related to the relative stoichiometry of the counterions.
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