Hybrid Uranyl-Carboxyphosphonate Cage Clusters

Two new hybrid uranyl-carboxyphosphonate cage clusters built from uranyl peroxide units were crystallized from aqueous solution under ambient conditions in approximately two months. The clusters are built from uranyl hexagonal bipyramids and are connected by employing a secondary metal linker, the 2-carboxyphenylphosphonate ligand. The structure of cluster <b>A</b> is composed of a ten-membered uranyl polyhedral belt that is capped on either end of an elongated cage by five-membered rings of uranyl polyhedra. The structure of cluster <b>B</b> consists of 24 uranyl cations that are arranged into 6 four-membered rings of uranyl polyhedra. Four of the corresponding topological squares are fused together to form a sixteen-membered double uranyl pseudobelt that is capped on either end by 2 topological squares. Cluster <b>A</b> crystallizes over a wide pH range of 4.6–6.8, while cluster <b>B</b> was isolated under narrower pH range of 6.9–7.8. Studies of their fate in aqueous solution upon dissolution of crystals by electrospray ionization mass spectrometry (ESI-MS) and small-angle X-ray scattering (SAXS) provide evidence for their persistence in solution. The well-established characteristic fingerprint from the absorption spectra of the uranium­(VI) cations disappears and becomes a nearly featureless peak; nonetheless, the two compounds fluoresce at room temperature