A Giant 3d‐4f Polyoxometalate Super‐Tetrahedron with High Proton Conductivity

The assembly of gigantic heterometallic metal clusters remains a great challenge for synthetic chemistry. Herein, based on the slow release strategy of lanthanide ions and in situ formation of lacunary polyoxometalates, two giant 3d-4f polyoxometalate inorganic clusters [LaNi₁₂ W₃₅ Sb₃ P₃ O₁₃₉ (OH)₆ ]^23- (LaNi₁₂ ) and [La₁₀ Ni₄₈ W₁₄₀ Sb₁₆ P₁₂ O₅₆₈ (OH)₂₄ (H₂ O)₂₀ ]^86- (La₁₀ Ni₄₈ ) are obtained. The nanoscopic inorganic cluster La₁₀ Ni₄₈ possesses a super tetrahedron structure, which can be viewed as assembly from four LaNi₁₂ molecules encapsulating a central [La₆ (SbO₃ )₄ (H₂ O)₂₀ ]⁶⁺ octahedron core. This giant aesthetic La₁₀ Ni₄₈ tetrahedron containing 214 metal ions is the largest 3d-4f cluster reported thus far in polyoxometalate system. More interestingly, the LaNi₁₂ and La₁₀ Ni₄₈ display high stability in solution and La₁₀ Ni₄₈ displays excellent proton conductivity.