Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations

Abstract

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Supramolecular Assembly of Geometrically Unstable Hybrid Organic–Inorganic Uranyl Peroxide Cage Clusters and Their Transformations

“…Each of these encapsulated K + cations are bonded to uranyl oxygen atoms and water (Figure 6c). A similar arrangement of the encapsulated counterions was reported earlier for Pb 8 O 6 4+ polyoxocations in U 24 , where Pb 2+ is also located under the hexagonal windows, 27 as well as the K cations in a salt of U 24 that contains both Li and K. 55 31 P NMR spectra were collected for room-temperature solutions of U 19 that had earlier been heated in sealed reactor vessels to soak temperatures from 40 to 160 °C for 8 h, as well as a control aged at room temperature for 8 h (Figure 7a). The disassembly of U 19 started in solutions heated to 40 °C, as indicated by the decrease of the peak intensity of BzDPA ligands contained in U 19 (signal A, 17.92 ppm) and increase of the peak intensity of disassociated BzDPA ligands (signal B, 12.20 ppm) in the solution.…”

“…Each of these encapsulated K + cations are bonded to uranyl oxygen atoms and water (Figure c). A similar arrangement of the encapsulated counterions was reported earlier for Pb 8 O 6 4+ polyoxocations in U 24 , where Pb 2+ is also located under the hexagonal windows, as well as the K cations in a salt of U 24 that contains both Li and K …”

“…Crystals of 2 , which contain the well-known U 24 cluster and K countercations, were isolated from aqueous solutions of U 19 after heat treatment from 60 to 100 °C. U 24 was first synthesized with Li + as the countercation and has since been reported containing Na + , Bi 3+ , Pb 2+ , and alkaline earth elements (Ca, Sr, Ba), − as well as combinations of Li/Na and Li/K . U 24 consists of 24 uranyl hexagonal bipyramids, each of which contains two peroxide ligands and two hydroxyl groups (Figure a) .…”

“…For example, U 20 and U 28 both have fullerene topologies, with the topology of U 28 consisting of six hexagons in addition to 12 pentagons (Figure a and b, U n represents a cluster containing n uranyl polyhedra) . U 24 adopts the sodalite topology consisting of topological squares and hexagons (Figure c). − U 32 has a topology that contains squares, pentagons, and hexagons (Figure d) …”

Polyoxocationic antimony oxide cluster with acidic protons

“…It is noted that sodalites [Al 6 Si 6 O 24 ] framework ( 28 ), uranium clusters [{(UO 2 )O 2 (OH)} 24 ] 24− ( 29 ), and M 8 P 16 (M = Cu, Ni) in clathrate compounds AM 2 P 4 (A = Sr, Ba) ( 30 ) have a structure with similar topology (truncated octahedron, 4 6 6 8 ) as the [Sb 24−δ O 36 ] cage in the outer shell of the HSbO clusters (fig. S6).…”