A spectroscopic, structural, and computational study of Ag–oxo interactions in Ag⁺/UO₂²⁺complexes

Abstract

The structural and spectroscopic properties of the uranyl cation is affected by close Ag–oxo interaction causing UO bond weakening.

A Spectroscopic and Computational Evaluation of Uranyl Oxo Engagement with Transition Metal Cations

“…A typical ρ bcp value for an unperturbed U�O bond is generally found between 0.300 and 0.320. 26,27 For compounds 3−5 and for the U�O bonds in 1 and 2 that do not interact closely with the Cd 2+ , the ρ bcp values all fall close to this range. For the U�O bonds interacting closely with the Cd 2+ , we see a significant decrease in the ρ bcp to <0.280.…”

“…In our previous work, 26,27 it was difficult to draw broader conclusions about the effects of equatorial coordination on metal-oxo interactions as we did not have large data sets for each metal, in particular since the Ag + /UO 2 2+ compounds (for which we had the largest data set) do not display significant trends to track. With the addition of this work, we can now compare within the 6 Pb 2+ /UO 2 2+ compounds previously published and the 5 Cd 2+ /UO 2 2+ compounds (in addition to the 12 compounds published by Thueŕy that supplemented the Pb 2+ /UO 2 2+ paper 57−61 ).…”

“…The axial U�O bonds have bond lengths of: U1�1.797( 7) Å (O1) and 1.782( 7) Å (O3), U2�1.780( 8) Å (O4) and 1.782( 8) Å (O5), U3�1.775( 8) Å (O6) and 1.797( 7) Å (O7), U4� 1.785( 8) Å (O8) and 1.766( 8) Å (O9), U5�1.775( 8) Å (O10) and 1.779( 7) Å (O11), U6�1.757( 9) Å (O12) and Cd 2+ Interactions with Uranyl Oxo Atoms. In our previous work on uranyl oxo interactions with Pb 2+ and Ag + , 26,27 we determined that crystallographic M n+ -oxo distances served as good indication of the strength of the interaction: shorter distances indicated stronger interactions. When comparing the interaction effects between the two different metals, the effects of Pb 2+ cations were much stronger than those of Ag + cations at comparable distances.…”

Uranyl ion coordination polymers with the dibenzobarrelene-based rac- and (R,R)-trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylate ligands

“…Due to their ability to be bonded to both carboxylates and aromatic rings, silver( i ) cations are able to bridge the hydrophilic and hydrophobic parts of different polymeric units and thus increase the overall periodicity, yet another example of the versatility of this cation and its interest in the synthesis of uranyl-based coordination polymers. 38…”

Heterometallic UO22+/Ag+ Complexes: Structural Design and Luminescence Properties

“…We included in our discussion 12 UO 2 2+ /Ag + compounds reported previously by our group. 4 These 23 compounds in total represent nearly one-third of the UO 2 2+ /Ag + compounds reported in the Cambridge Structural Database (as of February 2024) 24 and display a variety of topologies and coordination motifs, demonstrating the prolific nature of this synthetic strategy for forming heterometallic compounds. The synthetic design strategies described can be applied to a range of other metal cations and present an attractive platform for the study of heterometallic uranyl complexes.…”