Reaction of [Th(I)(NR₂)₃] (R = SiMe₃) (2) with KECPh₃ (E = O, S) affords the thorium chalcogenates, [Th(ECPh₃)(NR₂)₃] (3, E = O; 4, E = S), in moderate yields. Reductive deprotection of the trityl group from 3 and 4 by reaction with KC₈, in the presence of 18-crown-6, affords the thorium oxo complex, [K(18-crown-6)][Th(O)(NR₂)₃] (6), and the thorium sulphide complex, [K(18-crown-6)][Th(S)(NR₂)₃] (7), respectively. The natural bond orbital and quantum theory of atoms-in-molecules approaches are employed to explore the metal-ligand bonding in 6 and 7 and their uranium analogues, and in particular the relative roles of the actinide 5f and 6d orbitals.

Organic ligand complexes of lanthanide/actinide ions have been studied extensively for applications in nuclear fuel storage and recycling. Several complexes of 2,6-bis(2-benzimidazyl)pyridine (H2BBP) featuring the uranyl moiety have been reported recently, and the present study investigates the coordination characteristics of these complexes using density functional theory-based electronic structure analysis. In particular, with the aid of several computational models, the nonplanar equatorial coordination about uranyl, observed in some of the compounds, is studied and its origin traced to steric effects.

Soft X-ray spectromicroscopy at the O K-edge, U N_4,5-edges and Ce M_4,5-edges has been performed on focused ion beam sections of spent nuclear fuel for the first time, yielding chemical information on the sub-micrometer scale. To analyze these data, a modification to non-negative matrix factorization (NMF) was developed, in which the data are no longer required to be non-negative, but the non-negativity of the spectral components and fit coefficients is largely preserved. The modified NMF method was utilized at the O K-edge to distinguish between two components, one present in the bulk of the sample similar to UO₂ and one present at the interface of the sample which is a hyperstoichiometric UO_2+x species. The species maps are consistent with a model of a thin layer of UO_2+x over the entire sample, which is likely explained by oxidation after focused ion beam (FIB) sectioning. In addition to the uranium oxide bulk of the sample, Ce measurements were also performed to investigate the oxidation state of that fission product, which is the subject of considerable interest. Analysis of the Ce spectra shows that Ce is in a predominantly trivalent state, with a possible contribution from tetravalent Ce. Atom probe analysis was performed to provide confirmation of the presence and localization of Ce in the spent fuel.

Previous magnetic, spectroscopic, and theoretical studies of cerocene, Ce(C₈H₈)₂, have provided evidence for non-negligible 4f-electron density on Ce and implied that charge transfer from the ligands occurs as a result of covalent bonding. Strong correlations of the localized 4f-electrons to the delocalized ligand π-system result in emergence of Kondo-like behavior and other quantum chemical phenomena that are rarely observed in molecular systems. In this study, Ce(C₈H₈)₂ is analyzed experimentally using carbon K-edge and cerium M_5,4-edge X-ray absorption spectroscopies (XAS), and computationally using configuration interaction (CI) calculations and density functional theory (DFT) as well as time-dependent DFT (TDDFT). Both spectroscopic approaches provide strong evidence for ligand → metal electron transfer as a result of Ce 4f and 5d mixing with the occupied C 2p orbitals of the C₈H₈ ^2- ligands. Specifically, the Ce M_5,4-edge XAS and CI calculations show that the contribution of the 4f¹, or Ce³⁺, configuration to the ground state of Ce(C₈H₈)₂ is similar to strongly correlated materials such as CeRh₃ and significantly larger than observed for other formally Ce⁴⁺ compounds including CeO₂ and CeCl₆ ^2-. Pre-edge features in the experimental and TDDFT-simulated C K-edge XAS provide unequivocal evidence for C 2p and Ce 4f covalent orbital mixing in the δ-antibonding orbitals of e_2u symmetry, which are the unoccupied counterparts to the occupied, ligand-based δ-bonding e_2u orbitals. The C K-edge peak intensities, which can be compared directly to the C 2p and Ce 4f orbital mixing coefficients determined by DFT, show that covalency in Ce(C₈H₈)₂ is comparable in magnitude to values reported previously for U(C₈H₈)₂. An intuitive model is presented to show how similar covalent contributions to the ground state can have different impacts on the overall stability of f-element metallocenes.

Predictable stereoselective formation of supramolecular assembly is generally believed to be an important but complicated process. Here, we show that point chirality of a ligand decisively influences its supramolecular assembly behavior. We designed three closely related chiral ligands with different point chiralities, and observe their self-assembly into europium (Eu) tetrametallic tetrahedral cages. One ligand exhibits a highly diastereoselective assembly into homochiral (either ΔΔΔΔ or ΛΛΛΛ) Eu tetrahedral cages whereas the two other ligands, with two different approaches of loosened point chirality, lead to a significant breakdown of the diastereoselectivity to generate a mixture of (ΔΔΔΔ and ΛΛΛΛ) isomers. The cages are highly emissive (luminescence quantum yields of 16(1) to 18(1)%) and exhibit impressive circularly polarized luminescence properties (|g _lum|: up to 0.16). With in-depth studies, we present an example that correlates the nonlinear enhancement of the chiroptical response to the nonlinearity dependence on point chirality.