Synthesis, Structure, and Solid-State Transformation Studies of Phosphonoacetate Based Hybrid Compounds of Uranium and Thorium

Abstract

Three new phosphonoacetate hybrid frameworks based on the actinide elements uranium and thorium have been synthesized. The compounds [C(4)N(2)H(14)][(UO(2))(2)(O(3)PCH(2)COO)(2)] x H(2)O, I, [C(4)N(2)H(14)][(UO(2))(2)(C(2)O(4))(O(3)PCH(2)COOH)(2)], II, and Th(H(2)O)(2)(O(3)PCH(2)COO)(C(2)O(4))(0.5) x H(2)O, III, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units. Compound II has been prepared using a solvent-free approach, by a solid state reaction at 150 degrees C. It has been shown that II can also be prepared through a room temperature mechanochemical (grinding) route. The layer arrangement in III closely resembles to that observed in I. The compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and fluorescence studies.

Mixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity

“…7 As a result of this superimposition, metrical parameters describing the carbonate unit cannot be reliably reported, however, the rest of the structure can be accurately described. Th( [32][33][34][35][36] The Th-O oxalate bond distances in 4 lie just outside the lower range of those found in the latter (2.481(2)-2.578(7) Å), whilst the O-C oxalate bond distances in 4 are above the upper range of those found in the inorganic oxalates (1.242(3)-1.261(4) Å). The Th1-O1 and Th1-O2 bond distances are virtually identical (2.473(2) and 2.475(3) Å respectively), as are the O1-C001 and O2-C001 bond distances (1.264(4) and 1.260(4) Å respectively).…”

“…The bond between C001 and C001′ (symmetry generated) is single in nature, at 1.518(7) Å. There are no other Th(IV) oxalates supported by metallocene frameworks reported in the literature, however, several inorganic thorium oxalates have been reported containing bridging oxalate moieties as part of larger structural frameworks, i.e.Th(C 2 O 4 ) 2 (H 2 O) 2 • 2H 2 O [32][33][34][35][36]. The Th-O oxalate bond distances in 4 lie just outside the lower range of those found in the latter (2.481(2)-2.578(7) Å), whilst the O-C oxalate bond distances in 4 are above the upper range of those found in the inorganic oxalates (1.242(3)-1.261(4) Å).…”

Structural and spectroscopic characterization of two new layered uranyl(VI) p-xylenediphosphonate compounds synthesized via ionothermal method

“…The crystal chemistry of actinide phosphonates is an important subfield of metal phosphonates, where major attention was paid to uranium [13][14][15][16][17][18][19] and thorium [20][21][22], with only a few neptunium [22][23][24], plutonium [25][26][27][28], and americium [28] complexes. Layered structure is always observed in uranyl phosphonates, due to the nature of equatorial coordination sites (from four to six) of the uranyl ion, leading the structure to 2D topologies [19,[29][30][31][32][33][34].…”

High Uptake of ReO4− and CO2 Conversion by a Radiation‐Resistant Thorium–Nickle [Th48Ni6] Nanocage‐Based Metal–Organic Framework

“…Since O'Hare et al. reported the first Th‐MOF in 2003, other Th‐MOFs, especially the stable Th 6 ‐cluster with carboxylate ligands, have also been synthesized in which gas absorption and ion exchange were investigated . However, heterometallic MOFs containing Th and d‐block TM ions have not been reported to date.…”