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Issue 4, 2012
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Observation and investigation of the uranyl tetrafluoride dianion (UO2F42−) and its solvation complexes with water and acetonitrile

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Abstract

Bare uranyl tetrafluoride (UO2F42−) and its solvation complexes by one and two water or acetonitrile molecules have been observed in the gas phase using electrospray ionization and investigated by photoelectron spectroscopy and ab initio calculations. The isolated UO2F42− dianion is found to be electronically stable with an adiabatic electron binding energy of 1.10 ± 0.05 eV and a repulsive Coulomb barrier of ∼2 eV. Photoelectron spectra of UO2F42− display congested features due to detachment from U–O bonding orbitals and F 2p lone pairs. Solvated complexes by H2O and CH3CN, UO2F4(H2O)n2− and UO2F4(CH3CN)n2− (n = 1, 2), are also observed and their photoelectron spectra are similar to those of the bare UO2F42− dianion, suggesting that the solvent molecules are coordinated to the outer sphere of UO2F42− with relatively weak interactions between the solvent molecules and the dianion core. Both DFT and CCSD(T) calculations are performed on UO2F42− and its solvated species to understand the electronic structure of the dianion core and solute–solvent interactions. The strong U–F interactions with partial (d–p)π bonding are shown to weaken the U[double bond, length as m-dash]O bonds in the [O[double bond, length as m-dash]U[double bond, length as m-dash]O]2+ unit. Each H atom in the water molecules forms a H-bond to a F atom in the equatorial plane of UO2F42−, while each CH3CN molecule forms three H-bonds to two F ligands and one axial oxygen.

Graphical abstract: Observation and investigation of the uranyl tetrafluoride dianion (UO2F42−) and its solvation complexes with water and acetonitrile

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Supplementary files

Article information


Submitted
11 Dec 2011
Accepted
23 Dec 2011
First published
04 Jan 2012

Chem. Sci., 2012,3, 1137-1146
Article type
Edge Article

Observation and investigation of the uranyl tetrafluoride dianion (UO2F42−) and its solvation complexes with water and acetonitrile

P. D. Dau, J. Su, H. Liu, J. Liu, D. Huang, J. Li and L. Wang, Chem. Sci., 2012, 3, 1137
DOI: 10.1039/C2SC01052F

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