Assembly of actinyl cations, [AnO2]2+, (where An = U(VI), Np(VI) and Pu(VI)) into desired, crystalline architectures is of broad interest owing to the relevance to spent nuclear fuel stewardship, waste forms, separations and environmental transport. Our efforts have historically focused on the use of carboxylate and phosphonate based ligands to generate [AnO2]2+ based hybrid materials of higher structural dimensionality. More recently, however, we have focused on molecular materials wherein [AnO2]2+ species feature fixed first coordination spheres, and are in turn assembled through non-covalent interactions provided by judiciously placed synthons in (for example) the second coordination sphere. Presented will be an overview of two distinct approaches- the first features room temperature assembly in aqueous, high-anion media to generate [AnO2X4(H2O)m]n- (X = Cl, Br, NCS; m = 0,1; n = 2,3) anions, followed by assembly via hydrogen and halogen bond donating organic cations. The second utilizes chelating ligands (e.g. terpyridine, phenanthroline) under hydrothermal conditions to ‘cap’ the first coordination sphere, which not only prevents hydrolysis, but also allows for introduction of ligands functionalized for non-covalent interactions. Assembly proceeds as above, yet with additional opportunities to engage the nominally terminal ‘Oyl’ oxygen atoms via halogen-based interactions.

Tips and tricks for solid state assembly of actinyl cations

254th National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.