Assembly of Lanthanide-Containing Tungstotellurates(VI): Syntheses, Structures, and Catalytic Properties

Lanthanide (Ln)-containing polyoxometalates (POMs) have attracted particular attention owing to their structural diversity and potential applications in luminescence, magnetism, and catalysis. Herein three types of Ln-containing tungstotellurates(VI) (Ln = Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, Yb³⁺, and Lu³⁺), dimeric (DMAH) [H_22- {Ln(H₂O)₃[TeW₁₇O₆₁]}₂]^·mH₂O (abbreviated as {Ln₂Te₂W₃₄}; DMAH⁺ = dimethylammonium), mono-substituted (DMAH)₇Na₂{H₂Ln(H₂O)₄[TeW₁₇O₆₁]}^·mH₂O (abbreviated as {LnTeW₁₇}), and three-dimensional (3D) inorganic frameworks (DMAH) {H_3- Ln(H₂O)₄[TeW₆O₂₄]}^·mH₂O (abbreviated as {LnTeW₆}), have been synthesized by using simple metal salts and characterized by single-crystal X-ray diffraction and other routine techniques. Interestingly, the assembly of these POMs is pH dependent. Using the same starting materials, {Ln₂Te₂W₃₄} were obtained at pH 1.7, where two Dawson-like monovacant [TeW₁₇O₆₁]^14- are linked by two Ln³⁺ ions; mono-substituted Dawson-like {LnTeW₁₇} were isolated at pH 1.9, and 3D inorganic framework {LnTeW₆} based on Anderson-type [TeW₆O₂₄]^6- were formed at pH 2.3. It was also found that the assembly of Ln-containing POMs depends on the type of Ln³⁺ ions. The three types of POMs can be prepared by using Ln³⁺ ions with a relatively smaller ionic radius, such as Tb³⁺-Lu³⁺, while the use of Ln³⁺ ions (La³⁺-Eu³⁺) results in the formation of precipitation or {TeW₁₈O₆₂} clusters. Furthermore, three {LnTeW₆} (Ln = Tb³⁺, Er³⁺, Lu³⁺) were used as Lewis acid catalysts for the cyanosilylation of benzaldehydes, and their catalytic activity decreases with the decrease of Ln³⁺ ionic radius, giving the order: {TbTeW₆} > {ErTeW₆} > {LuTeW₆}. Notably, {TbTeW₆} is stable to leaching and can be reused for five cycles without a significant loss of its activity.