Synthesis, characterization, and high-pressure studies of a 3D berkelium(iii) carboxylate framework material

Abstract

A berkelium(III) mellitate, Bk2[C6(CO2)6](H2O)8∙2H2O, was synthesized and rapidly crystallized by reacting mellitic acid, C6(CO2H)6, and BkBr3∙nH2O in an aqueous medium. Single crystal X-ray diffraction shows that the compound crystallizes as...

Molecular Dynamics and Free Energy Calculations of Dicyclohexano-18-crown-6 Diastereoisomers with Sm2+, Eu2+, Dy2+, Yb2+, Cf2+, and Three Halide Salts in Tetrahydrofuran and Acetonitrile Using the AMOEBA Force Field

“…This observation is displayed in Figure S5, where if a trendline is built off of the Dy 2+ –X and Yb 2+ –X and the Cf 2+ –X interaction is placed in the middle, the Cf 2+ –X interactions with a harder Lewis acid Cl – fall on the trendline, while the softer Lewis acid I – falls below it. Similar trends have been observed where actinide–ligand bond distances are lanthanide-like with hard donor atoms , and not with soft donor atoms. , Again, following Ln trends for soft bases, where actinides stay below the trendline, the same behavior is observed here (Figure S5) for both diastereoisomers, which is an indicative of a good agreement between our proposed AMOEBA potentials for lanthanides and experimental data.…”

Advances and perspectives of actinide chemistry fromex situhigh pressure and high temperature chemical studies

“…The study highlighted the complexity of curium bonding, particularly covalent interactions at high pressure and the unexpected further impact it has on the ligands. Similar results were also reported by Sperling et al [98][99][100] on related americium in addition to similar berkelium and californium compounds by like methods highlighting both the sharp departure in bonding behaviour compared to non-actinide variants. Paucities of information still remain for the transuranics under pressure both from the understand-…”

Two Neptunium(III) Mellitate Coordination Polymers: Completing the Series Np–Cf of Trans-Uranic An(III) Mellitates

“…With the synthesis of Np-1α and Np-1β , there is now a complete series of crystallographically characterized mellitate complexes of the trans-uranic actinides for which bulk studies can be performed, of which there are no examples that we are aware of. The average M–O bond lengths of each published actinide and lanthanide mellitate complex − are plotted against the 6-coordinate ionic radii as calculated by Shannon in Figure S9 . Although the ions are 9-coordinate, this ionic radius has not been calculated for all the actinides.…”

“…This indicates that the bonding is generally driven by electrostatic interactions as in the lanthanide series, even in the earlier actinides like plutonium or neptunium which have the least localized f -electrons of the trans-uranic actinides. Although the 5 f orbitals are engaging in bonding to some degree more than in the lanthanides as indicated by high-pressure studies of americium, curium, berkelium, and californium, − it does not appear to affect the bonding at ambient pressure by a substantial amount. This emphasizes that differences in bonding in the actinides when compared to lanthanides are very much driven by the ligand complexing with the ion.…”

“…We have previously reported a series of trivalent actinide mellitate coordination polymers from plutonium to californium. − In this study, we present the synthesis and characterization of two trivalent neptunium mellitate compounds that are isomorphous to the plutonium mellitates, thereby completing the series of transuranic actinides for which experiments can currently be carried out on a macroscopic scale. One of the isolated morphologies is indefinitely air stable, while the other slowly oxidizes over several months.…”