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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. [ABSTRACT FROM AUTHOR]

A series of polyoxometalates (POMs) that incorporate the highest-nuclearity Ln clusters that have been observed in such structures to date (Ln26 , Ln=La and Ce) are described, which exhibit giant multishell configurations (Ln⊂W6⊂Ln26⊂W100). Their structures are remarkably different from known giant POMs that feature multiple Ln ions. In particular, the incorporated Ln-O clusters with a nuclearity of 26 are significantly larger than known high-nuclearity (≤10) Ln-O clusters in POM chemistry. Furthermore, they also contain the largest number of La and Ce centers for any POM reported to date and represent a new kind of rare giant POMs with more than 100 W atoms. Interestingly, the La26-containing POM can undergo a single-crystal to single-crystal structural transformation in the presence of various transition-metal ions, such as Cu2+, Co2+, and Ni2+, from an inorganic molecular nanocluster into an inorganic-organic hybrid extended framework that is built from POM building blocks with even higher-nuclearity La28 clusters bridged by transition-metal complexes. [ABSTRACT FROM AUTHOR]

The first series of niobium-tungsten-lanthanide (Nb-W-Ln) heterometallic polyoxometalates {Ln12W12O36(H2O)24(Nb6O19)12} (Ln=Y, La, Sm, Eu, Yb) have been obtained, which are comprised of giant cluster-in-cluster-like ({Ln12W12}-in-{Nb72}) structures built from 12 hexaniobate {Nb6O19} clusters gathered together by a rare 24-nuclearity sodalite-type heterometal-oxide cage {Ln12W12O36(H2O)24}. The Nb-W-Ln clusters present the largest multi-metal polyoxoniobates and a series of rare high-nuclearity 4d-5d-4f multicomponent clusters. Furthermore, the giant Nb-W-Ln clusters may be isolated as discrete inorganic alkali salts and can be used as building blocks to form high-dimensional inorganic-organic hybrid frameworks. [ABSTRACT FROM AUTHOR]