Solvent-induced assembly and photocatalytic properties of atomically precise tellurotungstate-templated Ag clusters

Atomically precise polyoxometalate (POM)-templated Ag clusters represent an emerging class of materials featuring well-defined structures and tunable functionalities. However, tellurotungstates have never been exploited as anionic templates for constructing high-nuclearity Ag clusters. Herein, we report two structurally new Ag clusters, [Ag₆₀(TeW₆O₂₄)₂(^tBuCC)₃₆(NO₃)₁₀Cl₂]·38CH₃CN (Ag60) and [Ag₄₆(TeW₁₃O₄₆)₂(^tBuCC)₂₄(NO₃)₂(CH₃CN)₈]·24CH₃CN (Ag46), successfully synthesized via a facile solvothermal method using tellurotungstates as in situ-generated templates. Notably, both POM templates, [Te₂W₁₂O₄₈]¹²⁻ and [Te₂W₂₆O₉₂]²⁰⁻, originate from the [TeW₉O₃₃]⁸⁻ ligands under different self-assembly conditions. The structures were characterized by Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction (SCXRD). SCXRD reveals that Ag60 adopts a peanut-shaped core–shell architecture encapsulating a {Te₂W₁₂O₄₈} unit, whereas Ag46 features a chair-shaped silver ring templated by a dumbbell-shaped {Te₂W₂₆O₉₂} chain. Photocatalytic experiments reveal that both clusters possess excellent photocatalytic performance for H₂O₂ production.