U(V) Stabilization via Aliovalent Incorporation of Ln(III) into Oxo‐salt Framework

Pentavalent uranium compounds are key components of uranium‘s redox chemistry and play important roles in environmental transport. Despite this, well‐characterized U(V) compounds are scarce primarily because of their instability with respect to disproportionation to U(IV) and U(VI). In this work, we provide an alternate route to incorporation of U(V) into a crystalline lattice where different oxidation states of uranium can be stabilized through the incorporation of secondary cations with different sizes and charges. We show that iriginite‐based crystalline layers allow for systematically replacing U(VI) with U(V) through aliovalent substitution of 2+ alkaline‐earth or 3+ rare‐earth cations as dopant ions under high‐temperature conditions, specifically Ca(UVIO2)W4O14 and Ln(UVO2)W4O14 (Ln=Nd, Sm, Eu, Gd, Yb). Evidence for the existence of U(V) and U(VI) is supported by single‐crystal X‐ray diffraction, high energy resolution X‐ray absorption near edge structure, X‐ray photoelectron spectroscopy, and optical absorption spectroscopy. In contrast with other reported U(V) materials, the U(V) single crystals obtained using this route are relatively large (several centimeters) and easily reproducible, and thus provide a substantial improvement in the facile synthesis and stabilization of U(V). Ln(UVO2)W4O14 series are the inaugural materials to structurally integrate pentavalent uranium with rare‐earth metals, featuring a unique U−Ln cation interaction. This occurs when Ln3+ ions replace Ca2+ in the crystal, they add extra positive charge, causing a charge imbalance that reduces uranium from U(VI) to U(V).