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Neural network potentials (NNPs) trained against density functional theory (DFT) are capable of reproducing the potential energy surface at a fraction of the computational cost. However, most NNP implementations focus on energy and forces. In this work, we modified the NNP model introduced by Behler and Parrinello to predict Fermi energy, band edges, and partial density of states of Cu 2 O. Our NNP can reproduce the DFT potential energy surface and properties at a fraction of the computational cost. We used our NNP to perform molecular dynamics (MD) simulations and validated the predicted properties against DFT calculations. Our model achieved a root mean squared error of 16 meV for the energy prediction. Furthermore, we show that the standard deviation of the energies predicted by the ensemble of training snapshots can be used to estimate the uncertainty in the predictions. This allows us to switch from the NNP to DFT on-the-fly during the MD simulation to evaluate the forces when the uncertainty is high. 

We report a rare example of the direct alkylation of the surface of a plenary polyoxometalate cluster by leveraging the increased nucleophilicity of vanadium oxide assemblies. Addition of methyl trifluoromethylsulfonate (MeOTf) to the parent polyoxovanadate cluster, [V 6 O 13 (TRIOL R ) 2 ] 2− (TRIOL = tris(hydroxymethyl)methane; R = Me, NO 2 ) results in functionalisation of one or two bridging oxide ligands of the cluster core to generate [V 6 O 12 (OMe)(TRIOL R ) 2 ] 1− and [V 6 O 11 (OMe) 2 (TRIOL R ) 2 ] 2− , respectively. Comparison of the electronic absorption spectra of the functionalised and unfunctionalised derivatives indicates the decreased overall charge of the complex results in a decrease in the energy required for ligand to metal charge transfer events to occur, while simultaneously mitigating the inductive effects imposed by the capping TRIOL ligand. Electrochemical analysis of the family of organofunctionalised polyoxovanadate clusters reveals the relationship of ligand environment and the redox properties of the cluster core: increased organofunctionalisation of the surface of the vanadium oxide assembly translates to anodic shifts in the reduction events of the Lindqvist ion. Overall, this work provides insight into the electronic effects induced upon atomically precise modifications to the surface structure of nanoscopic, redox-active metal oxide assemblies. 

Addition of [UI 2 (THF) 3 (μ-OMe)] 2 ·THF (2·THF) to THF solutions containing 6 equiv. of K[C 14 H 10 ] generates the heteroleptic dimeric complexes [K(18-crown-6)(THF) 2 ] 2 [U(η 6 -C 14 H 10 )(η 4 -C 14 H 10 )(μ-OMe)] 2 ·4THF (118C6·4THF) and {[K(THF) 3 ][U(η 6 -C 14 H 10 )(η 4 -C 14 H 10 )(μ-OMe)]} 2 (1THF) upon crystallization of the products in THF in the presence or absence of 18-crown-6, respectively. Both 118C6·4THF and 1THF are thermally stable in the solid-state at room temperature; however, after crystallization, they become insoluble in THF or DME solutions and instead gradually decompose upon standing. X-ray diffraction analysis reveals 118C6·4THF and 1THF to be structurally similar, possessing uranium centres sandwiched between bent anthracenide ligands of mixed tetrahapto and hexahapto ligation modes. Yet, the two complexes are distinguished by the close contact potassium-arenide ion pairing that is seen in 1THF but absent in 118C6·4THF, which is observed to have a significant effect on the electronic characteristics of the two complexes. Structural analysis, SQUID magnetometry data, XANES spectral characterization, and computational analyses are generally consistent with U( iv ) formal assignments for the metal centres in both 118C6·4THF and 1THF, though noticeable differences are detected between the two species. For instance, the effective magnetic moment of 1THF (3.74 μ B ) is significantly lower than that of 118C6·4THF (4.40 μ B ) at 300 K. Furthermore, the XANES data shows the U L III -edge absorption energy for 1THF to be 0.9 eV higher than that of 118C6·4THF, suggestive of more oxidized metal centres in the former. Of note, CASSCF calculations on the model complex {[U(η 6 -C 14 H 10 )(η 4 -C 14 H 10 )(μ-OMe)] 2 } 2− (1*) shows highly polarized uranium–arenide interactions defined by π-type bonds where the metal contributions are primarily comprised by the 6d-orbitals (7.3 ± 0.6%) with minor participation from the 5f-orbitals (1.5 ± 0.5%). These unique complexes provide new insights into actinide–arenide bonding interactions and show the sensitivity of the electronic structures of the uranium atoms to coordination sphere effects.