Homoleptic uranium(IV) amidate complexes have been synthesized and applied as single-source molecular precursors for the chemical vapor deposition of UO₂ thin films. These precursors decompose by alkene elimination to give highly crystalline phase-pure UO₂ films with an unusual branched heterostructure.

EXAFS provides the capability to interrogate nanoparticle (NP) structure in atomistic detail without relying on long-range crystallinity. There is a limitation in that EXAFS provides averaged structural information, making it difficult to separate a small amount of heterogeneous structure from bulk. In this work, models were developed to extract surface-specific information from conventional EXAFS measurements collected on UO2 NPs of varying size. Specifically, the surface terminating species of UO2 NPs was determined from comparison of coordination numbers with geometric models while the origin of static disorder was interrogated from user-defined simulations. Results show that the degree of oxygenation on the NP surface does not significantly deviate from bulk surface and that static disorder is highly enhanced in NP surface layers but cannot be attributed to surface relaxation effects alone. The approach described herein has the potential to be adapted to a range of inorganic NP systems to interrogate surface structure.

Two-electron reduction of the amidate-supported U(III) mono(arene) complex U(TDA)₃ (2) with KC₈ yields the anionic bis(arene) complex [K[2.2.2]cryptand][U(TDA)₂] (3) (TDA = N-(2,6-di-isopropylphenyl)pivalamido). EPR spectroscopy, magnetic susceptibility measurements, and calculations using DFT as well as multireference CASSCF methods all provide strong evidence that the electronic structure of 3 is best represented as a 5f⁴ U(II) metal center bound to a monoreduced arene ligand. Reactivity studies show 3 reacts as a U(I) synthon by behaving as a two-electron reductant toward I₂ to form the dinuclear U(III)-U(III) triiodide species [K[2.2.2]cryptand][(UI(TDA)₂)₂(μ-I)] (6) and as a three-electron reductant toward cycloheptatriene (CHT) to form the U(IV) complex [K[2.2.2]cryptand][U(η⁷-C₇H₇)(TDA)₂(THF)] (7). The reaction of 3 with cyclooctatetraene (COT) generates a mixture of the U(III) anion [K[2.2.2]cryptand][U(TDA)₄] (1-crypt) and U(COT)₂, while the addition of COT to complex 2 instead yields the dinuclear U(IV)-U(IV) inverse sandwich complex [U(TDA)₃]₂(μ-η⁸:η³-C₈H₈) (8). Two-electron reduction of the homoleptic Th(IV) amidate complex Th(TDA)₄ (4) with KC₈ gives the mono(arene) complex [K[2.2.2]cryptand][Th(TDA)₃(THF)] (5). The C-C bond lengths and torsion angles in the bound arene of 5 suggest a direduced arene bound to a Th(IV) metal center; this conclusion is supported by DFT calculations.

Uranium nitride complexes are attractive targets for chemists as molecular models for the bonding, reactivity, and magnetic properties of next-generation nuclear fuels, but these molecules are uncommon and can be difficult to isolate due to their high reactivity. Here, we describe the synthesis of three new multinuclear uranium nitride complexes, [U(BCMA)₂]₂(μ-N)(μ-κ¹:κ¹-BCMA) (7), [(U(BIMA)₂)₂(μ-N)(μ-NⁱPr)(K₂(μ-η³:η³-CH₂CHNⁱPr)]₂ (8), and [U(BIMA)₂]₂(μ-N)(μ-κ¹:κ¹-BIMA) (9) (BCMA = N,N-bis(cyclohexyl)methylamidinate, BIMA = N,N-bis(iso-propyl)methylamidinate), from U(III) and U(IV) amidinate precursors. By varying the amidinate ligand substituents and azide source, we were able to influence the composition and size of these nitride complexes. ¹⁵N isotopic labeling experiments confirmed the bridging nitride moieties in 7-9 were formed via two-electron reduction of azide. The tetra-uranium cluster 8 was isolated in 99% yield via reductive cleavage of the amidinate ligands; this unusual molecule contains nitrogen-based ligands with formal 1-, 2-, and 3- charges. Additionally, chemical oxidation of the U(IV) precursor U(N₃)(BCMA)₃ yielded the cationic U(V) species [U(N₃)(BCMA)₃][OTf]. Magnetic susceptibility measurements confirmed a U(IV) oxidation state for the uranium centers in the three nitride-bridged complexes and provided a comparison of magnetic behavior in the structurally related U(III)-U(IV)-U(V) series U(BCMA)₃, U(N₃)(BCMA)₃, and [U(N₃)(BCMA)₃][OTf]. At 240 K, the magnetic moments in this series decreased with increasing oxidation state, i.e., U(III) > U(IV) > U(V); this trend follows the decreasing number of 5f valence electrons along this series.

We report the synthesis of four homoleptic thorium(iv) amidate complexes as single-source molecular precursors for thorium dioxide. Each can be sublimed at atmospheric pressure, with the substituents on the amidate ligands significantly impacting their volatility and thermal stability. These complexes decompose via alkene elimination to give ThO2 without need for a secondary oxygen source. ThO2 samples formed from pyrolysis of C-alkyl amidates were found to have higher purity and crystallinity than ThO2 samples formed from C-aryl amidates.

We report the structural properties of ultra-small ThO₂ and UO₂ nanoparticles (NPs), which were synthesized without strong binding surface ligands by employing a covalent organic framework (COF-5) as an inert template. The resultant NPs were used to observe how structural properties are affected by decreasing grain size within bulk actinide oxides, which has implications for understanding the behavior of nuclear fuel materials. Through a comprehensive characterization strategy, we gain insight regarding how structure at the NP surface differs from the interior. Characterization using electron microscopy and small-angle X-ray scattering indicates that growth of the ThO₂ and UO₂ NPs was confined by the pores of the COF template, resulting in sub-3 nm particles. X-ray absorption fine structure spectroscopy results indicate that the NPs are best described as ThO₂ and UO₂ materials with unpassivated surfaces. The surface layers of these particles compensate for high surface energy by exhibiting a broader distribution of Th-O and U-O bond distances despite retaining average bond lengths that are characteristic of bulk ThO₂ and UO₂. The combined synthesis and physical characterization efforts provide a detailed picture of actinide oxide structure at the nanoscale, which remains highly underexplored compared to transition metal counterparts.