High‐dimensional Polyoxoniobates Constructed from Lanthanide‐incorporated High‐nuclear {[Ln(H2O)4]3[Nb24O69(H2O)3]2} Secondary Building Units

In this work, two rare high‐dimensional polyoxoniobates with formulas of H9[Cu(en)(H2O)2][Cu(en)2]8[Dy(H2O)4]3[Nb24‐O69(H2O)3]2 ⋅ 36H2O (1) and H9K[Cu(en)2(H2O)]5[Cu(en)2]4‐[Eu(H2O)4]3[Nb24O69(H2O)3]2 ⋅ 2en ⋅ 45H2O (2) have been obtained under hydrothermal conditions. These extended materials are constructed from lanthanide‐incorporated triangular‐prism‐like polyoxoniobate secondary building units (SBUs) {[Ln(H2O)4]3[Nb24O69(H2O)3]2} (Ln=Dy, Eu). 1 and 2 represent the first examples of high‐dimensional polyoxometalate materials based on such lanthanide‐incorporated triangular‐prism‐like polyoxoniobate SBUs. Furthermore, the proton conduction property and the luminescent emission of these materials were evaluated. Uncommon lanthanide‐incorporated triangular‐prism‐like high‐nuclear polyoxoniobate cluster secondary building units {[Ln(H2O)4]3[Nb24O69(H2O)3]2} (Ln=Dy, Eu) were introduced to construct two unusual high‐dimensional materials including a 3‐dimensional framework and a supramolecular framework based on 2‐D layers.