Publication | Open Access
Hierarchy of Pyrophosphate-Functionalized Uranyl Peroxide Nanocluster Synthesis
24
Citations
43
References
2017
Year
Herein, we report a new salt of a pyrophosphate-functionalized uranyl peroxide nanocluster {U<sub>24</sub>Pp<sub>12</sub>} (1) exhibiting O<sub>h</sub> molecular symmetry both in the solid and solution. Study of the system yielding 1 across a wide range of pH by single-crystal X-ray diffraction, small-angle X-ray scattering, and a combination of traditional <sup>31</sup>P and diffusion-ordered spectroscopy (DOSY) NMR affords unprecedented insight into the amphoteric chemistry of this uranyl peroxide system. Key results include formation of a rare binary {U<sub>24</sub>}·{U<sub>24</sub>Pp<sub>12</sub>} (3) system observed under alkaline conditions, and evidence of acid-promoted decomposition of {U<sub>24</sub>Pp<sub>12</sub>} (1) followed by spatial rearrangement and condensation of {U<sub>4</sub>} building blocks into the {U<sub>32</sub>Pp<sub>16</sub>} (2) cluster. Furthermore, <sup>31</sup>P DOSY NMR measurements performed on saturated solutions containing crystalline {U<sub>32</sub>Pp<sub>16</sub>} show only trace amounts (∼2% relative abundance) of the intact form of this cluster, suggesting a complex interconversion of {U<sub>24</sub>Pp<sub>12</sub>}, {U<sub>32</sub>Pp<sub>16</sub>}, and {U<sub>4</sub>Pp<sub>4-x</sub>} ions.
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