Issue 15, 2018

The oxidation of borohydrides by photoexcited [UO2(CO3)3]4−

Abstract

The carbonate ion is an effective quencher of uranyl(VI) luminescence and makes uranyl(VI) tricarbonate barely luminescent and photochemically inactive. We demonstrate here that photoexcited uranyl(VI) tricarbonate, *[UVIO2(CO3)3]4−, can however oxidize borohydrides (BH3X, X = H, CN) to give boric acid and H2 gas, reducing itself to [UVO2(CO3)3]5−. This hypothesis was supported by UV-vis and NMR spectroscopy as well as quantum chemical calculations. The charge transfer states associated with photoreduction processes were modelled by density functional theory calculations. These results suggest that the mechanism of photoreduction of [UVIO2(CO3)3]4− is similar to that of [UVIO2(H2O)5]2+ and that it occurs through a one-photon reduction process.

Graphical abstract: The oxidation of borohydrides by photoexcited [UO2(CO3)3]4−

Supplementary files

Article information

Article type
Communication
Submitted
09 Feb 2018
Accepted
05 Mar 2018
First published
05 Mar 2018

Dalton Trans., 2018,47, 5149-5152

The oxidation of borohydrides by photoexcited [UO2(CO3)3]4−

K. Takao and S. Tsushima, Dalton Trans., 2018, 47, 5149 DOI: 10.1039/C8DT00559A

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