Inlay

Despite decades of actinyl chemistry, genuinely bent actinyl structures remain rare beyond uranium. We report the first crystallographic characterization of a bent neptunyl(VI) complex, NpO2Cl2(phen)2, along with a linear plutonyl species that, unexpectedly, adopts the +V oxidation state. Coordination of two 1,10-phenanthroline ligands to NpO22+ enforces pronounced bending of the Oyl–Np–Oyl unit to 162° through steric clashes with the axial phenathroline ligand, representing the sharpest angle reported for any neptunyl(VI) complex. In contrast, synthesis with PuO22+ produces a reduced linear Pu(V) species, PuO2Cl(phen)2, underscoring the redox lability and the reluctance of plutonium to distort. Raman and IR spectra yield the first experimental stretching and interaction force constants for plutonyl(V). Comparison with values for plutonyl(VI) and bent and linear uranyl(VI) and neptunyl(VI) compounds shows that reduction perturbs the actinyl bond more than bending within one oxidation state. Electrochemical and spectroscopic studies clarify phenanthroline binding to Pu(VI) and the system’s reactivity. Quantum chemical calculations indicate that bending is energetically favored in the U–Np–Pu series, but the stabilization energy decreases as the actinide atomic number increases. NBO and QTAIM analyses reveal systematic trends: increasing 5f occupancy and decreasing An–Oyl bond covalency from U to Pu. These results demonstrate that ligand-induced bending in neptunyl(VI) species is not only electronically feasible but also synthetically achievable, though plutonyl(VI) is constrained by redox reactivity. This work expands the frontier of nonlinear actinyl chemistry and illuminates how structure, oxidation state, and electronic configuration interrelate across the actinyl series.

The purple membrane from Halobacterium salinarum archaea can unidirectionally transfer charge carriers in response to incident photons, even after separation from living cells. Upon integration with semiconductor nanoparticles, this isolated membrane forms a photosynthetic biohybrid system capable of abiotically and efficiently converting dinitrogen into ammonia under ambient conditions. The cover concept was developed by the authors to visualize this light-driven abiotic nitrogen fixation pathway. An initial sketch was generated using ChatGPT’s DALL·E tool and was subsequently refined and finalized using Adobe Photoshop. View the article.