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Issue 15, 2018
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The oxidation of borohydrides by photoexcited [UO2(CO3)3]4−

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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−

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The article was received on 09 Feb 2018, accepted on 05 Mar 2018 and first published on 05 Mar 2018

Article type: Communication
DOI: 10.1039/C8DT00559A
Citation: Dalton Trans., 2018,47, 5149-5152
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    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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