A Tri-U(VI)-Substituted Tellurotungstate with a Trigonal Bipyramidal {NaWU 3 } Core: Synthesis, Structure, and Catalytic Properties

A novel U(VI)-substituted tellurotungstate, Na₁₃H₆[{NaWU₃O₁₀(H₂O)₃}(B-α-TeW₉O₃₃)₃]·55H₂O (U₃TeW), was successfully synthesized through the reaction of trivacant Keggin precursors with 5f U(VI) ions. The compound was systematically characterized using various techniques. Structural analysis reveals that U₃TeW consists of three [B-α-TeW₉O₃₃]^8- fragments encapsulating a central heterometallic NaWU₃O₁₀(H₂O)₃ cluster with a trigonal bipyramidal geometry. Furthermore, U₃TeW exhibits remarkable photocatalytic activity in the visible-light-driven hydroacylation of dialkyl azodicarboxylates, enabling efficient C-N bond formation with excellent yields and broad substrate scope. This study provides a rare example of U(VI)-incorporated polyoxometalate-based photocatalysts applied in the field of C-H functionalization.