Yan-Jie Qi

Giant Hollow Heterometallic Polyoxoniobates with Sodalite-Type Lanthanide–Tungsten–Oxide Cages: Discrete Nanoclusters and Extended Frameworks

The first series of niobium-tungsten-lanthanide (Nb-W-Ln) heterometallic polyoxometalates {Ln12 W12 O36 (H2 O)24 (Nb6 O19 )12 } (Ln=Y, La, Sm, Eu, Yb) have been obtained, which are comprised of giant cluster-in-cluster-like ({Ln12 W12 }-in-{Nb72 }) structures built from 12 hexaniobate {Nb6 O19 } clusters gathered together by a rare 24-nuclearity sodalite-type heterometal-oxide cage {Ln12 W12 O36 (H2 O)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.

Composite Hybrid Cluster Built from the Integration of Polyoxometalate and a Metal Halide Cluster: Synthetic Strategy, Structure, and Properties

A step-by-step synthetic strategy, setting up a bridge between the polyoxometalate (POM) and metal halide cluster (MHC) systems, is demonstrated to construct an unprecedented composite hybrid cluster built up from one high-nuclearity cationic MHC [Cu8I6](2+) and eight Anderson-type anionic POMs [HCrMo6O18(OH)6](2-) cross-linked by a tripodal alcohol derivative.

Cluster Organic Frameworks Constructed from Heterometallic Supertetrahedral Cluster Secondary Building Units

The two novel cluster organic frameworks based on heterometallic supertetrahedral cluster secondary building units (SBUs) [Cd4Cu6(L)4(Ac)7(H2O)4](Ac)·7H2O (1) and [Mn4Cu6(L)4(Ac)4.5(H2O)9]CuCN(Ac)3.5·H2O (2), where H3L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol and Ac = CH3COO-, have been prepared under solvothermal conditions. 1 and 2 are the first cases of cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral cluster SBUs. Furthermore, 1 and 2 show an integration of magnetic properties and adsorption properties from both the heterometallic cluster secondary building units and the framework in a porous material.

Record High-Nuclearity Polyoxoniobates: Discrete Nanoclusters {Nb114}, {Nb81} and {Nb52}, and Extended Frameworks Based on {Cu3Nb78} and {Cu4Nb78}

A series containing the highest nuclearity polyoxoniobate (PONb) nanoclusters, ranging from dimers to tetramers, has been obtained. They include one 114-nuclear {Li8 ⊂Nb114 O316 }, one 81-nuclear {Li3 K⊂Nb81 O225 }, and one 52-nuclear {H4 Nb52 O150 }. The Nb nuclearity of these PONbs is remarkably larger than those of all known high-nuclearity PONbs (≤32). Furthermore, the introduction of 3d Cu2+ ions can lead to the generation of extended inorganic-organic hybrid frameworks built from novel, high-nuclearity, nanoscale heterometallic PONb building blocks {H3 Cu3 Nb78 O222 } or {H3 Cu4 (en)Nb78 O222 }. These building blocks also contain the largest number of Nb centers of any heterometallic PONbs reported to date. The synthesis of new-type PONbs has long been a challenging subject in PONb chemistry.

Incorporating cuprous-halide clusters and lanthanide clusters to construct Heterometallic cluster organic frameworks with luminescence and gas adsorption properties

A series of heterometallic cluster organic frameworks based on cuprous-halide Cu4I4 clusters and lanthanide clusters, [Ln2(H2O)8]2(Cu4I4)(pdc)4][NO3]4·solvent (1-Ln, Ln = Y, Tb, Eu, H2pdc = 3,5-pyridinedicarboxylic acid), have been successfully synthesized under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that 1-Ln show fascinating three-dimensional porous framework structures constructed from two dissimilar types of nanosized coordination cages. Gas sorption measurements indicate that 1-Ln show moderate gas uptake capacities. The UV/vis spectroscopy measurements reveal that 1-Ln are a class of potential materials for the removal of Cr2O72− from aqueous solution. Additionally, the luminescence properties of 1-Tb and 1-Eu have also been investigated.