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

Authors: Shu‐Rong Li, Hai‐Ying Wang, Hai‐Feng Su, Hui‐Jun Chen, Ming‐Hao Du, La‐Sheng Long, Xiang‐Jian Kong, Lan‐Sun Zheng

Abstract: 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 [LaNi₁₂W₃₅Sb₃P₃O₁₃₉(OH)₆]²³⁻ (LaNi₁₂) and [La₁₀Ni₄₈W₁₄₀Sb₁₆P₁₂O₅₆₈(OH)₂₄(H₂O)₂₀]⁸⁶⁻ (La₁₀Ni₄₈) are obtained. The nanoscopic inorganic cluster La₁₀Ni₄₈ possesses a super tetrahedron structure, which can be viewed as assembly from four LaNi₁₂ molecules encapsulating a central [La₆(SbO₃)₄(H₂O)₂₀]⁶⁺ octahedron core. This giant aesthetic La₁₀Ni₄₈ tetrahedron containing 214 metal ions is the largest 3d‐4f cluster reported thus far in polyoxometalate system. More interestingly, the LaNi₁₂ and La₁₀Ni₄₈ display high stability in solution and La₁₀Ni₄₈ displays excellent proton conductivity.

Full-Link: https://onlinelibrary.wiley.com/doi/10.1002/smtd.202000777