ic0c01080_si_001.pdf (461.49 kB)
Organic Functionalization of Uranyl Peroxide Clusters to Impact Solubility
journal contribution
posted on 2020-07-09, 19:45 authored by Mengyu Xu, Peter Eckard, Peter C. BurnsBenzene-1,2-diphosphonic
acid (Ppb) was introduced into the uranyl
peroxide cluster system, resulting in three Ppb-functionalized uranyl
peroxide clusters, (UO2)20(O2)20(C6H4P2O6)1040– (U20Ppb10), (UO2)26(O2)33(C6H4P2O6)638– (U26Ppb6), and (UO2)20(O2)24(C6H4P2O6)632– (U20Ppb6). Dissolution experiments were performed for the potassium
salts of U20Ppb10 and U26Ppb6, which revealed the capacity of U20Ppb10 to dissolve in the organic solvent dimethyl sulfoxide (DMSO). Unlike
U20Ppb10, the K salt of U26Ppb6 did not dissolve in DMSO but was more soluble in water, perhaps
due to the lower proportion of Ppb ligands in its structure. In this
work, U20Ppb10 and U20Ppb6 formed as potassium salts and both adopt the fullerene topology
of previously reported U20. U20 contains 20
uranyl peroxide units and encapsulates 12 Na cations. It is not possible
for unfunctionalized U20 to incorporate 12 K cations owing
to space constraints, as is the case in the new clusters reported
here. Transformation of U20Ppb10 in water over
time to produce U24 was observed, possibly owing to its
ability to incorporate K cations, which have been associated with
the formation of U24.