Formic acid interaction with the uranyl(vi) ion: structural and photochemical characterization

Lucks, Christian; Roßberg, André; Tsushima, Satoru; Foerstendorf, Harald; Fahmy, Karim; Bernhard, Gert

doi:10.1039/c3dt51711j

Cited by 29 publications

(23 citation statements)

References 30 publications

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“…An examination of crystal structures in the Cambridge Structural Database reveals that formate almost exclusively binds in a bridging bidentate fashion to the uranyl metal center. This observation is also supported by DFT calculations that demonstrate that a non‐bridging monodentate coordination exists only at lower pH values and with EXAFS studies showing that potential polymerization of the uranyl polyhedra occurs via bridging bidentate coordination . In the uranyl–formate compounds reported by Thuery, (H‐DABCO)[(UO 2 ) 3 (HCOO) 2 O(OH) 3 ] and Na 3 [(UO 2 ) 12 O 4 (OH) 12 (H 2 O) 2 (HCOO) 7 ] · 16H 2 O · 2cb6 (cb6 = cucurbit[6]uril), both O atoms on the formate ion coordinate to uranyl centers ,.…”

Section: Resultssupporting

confidence: 57%

Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within U^VI Glycine Compounds

et al. 2017

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U VI chemistry is dominated by the uranyl (UO 2 ) 2+ cation, in which the oxo group is essentially passivated by a triple bond to the metal center. Weak interactions between the oxo group Lewis acids or hydrogen-bond donors can be observed in extended solids, but there is little understanding of how the uranyl bond is affected by these additional forces. In the current study, the influence of charge-assisted hydrogen-bonding and crystallization effects on the uranyl oxo bond is explored through the synthesis and characterization of four uranyl compounds: [(UO 2 ) 3 (Gly) 2 (O) 2 (OH) 2 ](H 2 O) 1.5 (UG1b), [(UO 2 ) 4 (Gly) 3 -(For)(O) 3 (OH)](H 2 O) 6.5 (UGFA1a), [(UO 2 ) 8 (Gly) 6 (For) 2 (O) 6 (OH) 2 ]-(H 2 O) 10 (UGFA1b), and [(UO 2 ) 4 (Gly) 3 (O) 3 (OH) 2 ](HFor)(H 2 O) 9.45 [a]where S is representative of the bond valence or bond flux of each bond (expressed as valence units), R is the bond distance, R 0 is the Eur.

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Section: Resultssupporting

confidence: 57%

Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within U^VI Glycine Compounds

et al. 2017

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“…99 Further, the IR absorption spectrum of the deprotonated carboxylic acid in earlier reports depicted two strong bands within the spectral range of 1100− 1800 cm −1 . 100 The band at 1579 cm −1 was assigned to the antisymmetric COO stretching, while the band appearing at 1351 cm −1 was designated to the symmetric COO stretching vibrations of the carboxylate group. We determine the carboxylate vibrational frequencies corresponding to the positions of the highest intensity of the spectral peaks using the DFT-GGA functionals.…”

Section: Resultsmentioning

confidence: 99%

Dynamics of Ionic Liquid through Intrinsic Vibrational Probes Using the Dispersion-Corrected DFT Functionals

Biswas

Mallik

2021

J. Phys. Chem. B

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First principles molecular dynamics simulations have been utilized to study the spectral properties of the protic ionic liquid, methylammonium formate (MAF). All simulations were performed using density functional theory (DFT) and various van der Waals-corrected exchange–correlation functionals. We calculated the vibrational stretch frequency distributions, determined the time–frequency correlations of the intrinsic vibrational probes, the N–H and C–O modes in MAF, and the frequency–structure correlations. We also estimated the average hydrogen-bond lifetimes and orientation dynamics to capture the ultrafast spectral response. The spectroscopic signature of the N–H stretching vibrations using the Becke–Lee–Yang–Parr (BLYP) and Perdew–Burke–Ernzerhof (PBE) functionals displays a spectral shift in the lower frequency side, suggesting stronger hydrogen-bonding interactions represented by the gradient approximation functionals than the van der Waals (vdW)-corrected simulations. The carboxylate frequency profiles with the dispersion-corrected representations are almost similar without a significant difference in the normalized distributions. Besides, the COO stretching frequencies at the peak maxima positions of the PBE functionals exhibit a lesser deviation from the experimental data. Spectral diffusion dynamics of the intrinsic vibrational probes on the cationic and anionic sites of the ionic liquid proceed through a short time relaxation of the intact hydrogen bonds followed by an intermediate time constant and a longer time decay indicating the switchover of hydrogen bonds. Dispersion-corrected atom-centered one-electron potential (DCACP) correction added to the BLYP system slows down the picosecond time scales of frequency correlation and the time constants of rotational motion, lengthening the overall system dynamics. The observed trends in the time-dependent decays of frequency fluctuations and the orientation autocorrelation functions correlate with the structural interactions in liquid MAF and hydrogen-bond dynamics. In this study, we examine the predictions made by different density functional treatments comparing the results of the uncorrected BLYP and PBE representations with the semiempirical vdW methods of Grimme and matching our calculated data with the experimental observations.

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“…Specifically, bidentate coordination was used for carbonate, 24 nitrate, 25 and acetate. 26 For oxalate 27 and sulfate, 28 a chelate binding mode and unidentate coordination were used, respectively. Fig.…”

Section: B3lyp Versus Experimentsmentioning

confidence: 99%

On the “yl” bond weakening in uranyl(VI) coordination complexes

Tsushima

2011

Dalton Trans.

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The U-O(yl) triple bonds in the UO(2)(2+) aquo ion are known to be weakened by replacing the first shell water with organic or inorganic ligands. Weakening of the U-O(yl) bond may enhance the reactivity of "yl" oxygens and uranyl(VI) cation-cation interactions. Density functional theory calculations as well as previously published vibrational spectroscopic data have been used to study the origin of the U-O(yl) bond weakening in uranyl(VI) coordination complexes. Natural population analyses (NPA) revealed that the electron localization on the O(yl) 2p orbital is a direct measure of the U-O(yl) bond weakening, indicating that the bond weakening is correlated to the weakening of the U-O(yl) covalent bond and not that of the ionic bond. The Mulliken analysis gives poor results for uranium to ligand electron partitioning and is thus unreliable. Further analyses of molecular orbitals near the highest occupied molecular orbital (HOMO) show that both the σ and π donating abilities of the ligands may account for the U-O(yl) bond weakening. The mechanism of the bond weakening varies with coordinating ligand so that each case needs to be examined independently.

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Formic acid interaction with the uranyl(vi) ion: structural and photochemical characterization

Cited by 29 publications

References 30 publications

Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within U^VI Glycine Compounds

Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within U^VI Glycine Compounds

Dynamics of Ionic Liquid through Intrinsic Vibrational Probes Using the Dispersion-Corrected DFT Functionals

On the “yl” bond weakening in uranyl(VI) coordination complexes

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Formic acid interaction with the uranyl(vi) ion: structural and photochemical characterization

Cited by 29 publications

References 30 publications

Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within UVI Glycine Compounds

Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within UVI Glycine Compounds

Dynamics of Ionic Liquid through Intrinsic Vibrational Probes Using the Dispersion-Corrected DFT Functionals

On the “yl” bond weakening in uranyl(VI) coordination complexes

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Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within U^VI Glycine Compounds

Charge‐Assisted Hydrogen‐Bonding and Crystallization Effects within U^VI Glycine Compounds