Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag₁₂}‐in‐{W₇₆} Polyoxometalates under Supramolecular Control

Abstract

We report the time-resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one-pot reaction) of the form: [H(10+m)Ag18Cl(Te3W38O134)2]n, where n=1 and m=0 for compound 1 (after 4 days), n=2 and m=3 for compound 2 (after 10 days), and n=∞ and m=5 for compound 3 (after 14 days). The reaction is based upon the self-organization of two {Te3W38} units around a single chloride template and the formation of a {Ag12} cluster, giving a {Ag12}-in-{W76} cluster-in-cluster in compound 1, which further aggregates to cluster compounds 2 and 3 by supramolecular Ag-POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI-MS. Further, control experiments demonstrate the crucial role that TeO3(2-), Cl(-), and Ag(+) play in the self-assembly of compounds 1-3.

Controlling the Reactivity of the [P8W48O184]40− Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions

“…[16] All of these structures were based on transition metal complexes with the superlacunary {P 8 W 48 }cluster acting as al igand. [17] [18] Although these growth points have been noted as being occupied by both tungsten and other transition metals in previous publications, [16][17][18]20] no extended structures built upon these foundations have been reported.…”

{Nb288O768(OH)48(CO3)12}: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms

“…On the other hand, giant inorganic molecules have appealing structural features (for example,nanometer dimensions,m ultiple configurations,a nd high-nuclearity metal centers) associated with unusual physical properties that do not occur for smaller molecules. [1][2][3][4][5][6][7][8][9][10][11] Giant polyoxometalates (POMs) are of particular interest, as they are the largest inorganic molecules ever made, combined with fascinating structures and manifold applications in catalysis,m edicine,a nd material sciences. [3][4][5][6][7][8] Typically,M üllersg roup has achieved great success in creating giant polyoxomolybdates (POMos) during the past two decades,e stablishing as eries of incredibly large POMos with hundreds of Mo centers,s uch as {Mo 132 }, [4a] {Mo 154 }, [4b] {Mo 176 }, [4c] {Mo 248 }, [4d] and {Mo 368 }.…”

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

“…[5] Especially,t his strategy can allow access to ag reater level of self-assembly to form surprising giant high-nuclearity heterometallic POMs, [6][7][8] [8a,b,c,d] Since the first heteropolyoxoniobate [SiNb 12 O 40 ] 16À was reported by Nyman et al in 2002, [9] intensive efforts have been invested into development of novel heterometallic PONbs by the introduction of metals.N evertheless,t he integration of metals into PONbs remains largely undeveloped to date because the working pH region (ca. [5] Especially,t his strategy can allow access to ag reater level of self-assembly to form surprising giant high-nuclearity heterometallic POMs, [6][7][8] [8a,b,c,d] Since the first heteropolyoxoniobate [SiNb 12 O 40 ] 16À was reported by Nyman et al in 2002, [9] intensive efforts have been invested into development of novel heterometallic PONbs by the introduction of metals.N evertheless,t he integration of metals into PONbs remains largely undeveloped to date because the working pH region (ca.…”

“…Theintroduction of metals (for example,transition metals and lanthanides) into POMs is an effective strategy for construction of POMs with diverse chemical compositions, structures,a nd functionalities.F or instance,t his strategy has achieved great success in creating transition-metal-substituted polyoxotungstates. [5] Especially,t his strategy can allow access to ag reater level of self-assembly to form surprising giant high-nuclearity heterometallic POMs, [6][7][8] [8a,b,c,d] Since the first heteropolyoxoniobate [SiNb 12 O 40 ] 16À was reported by Nyman et al in 2002, [9] intensive efforts have been invested into development of novel heterometallic PONbs by the introduction of metals.N evertheless,t he integration of metals into PONbs remains largely undeveloped to date because the working pH region (ca. 10.5-12.5) of PONbs is incompatible with the solubility of most metal cations (acidic nature).…”

“…Herein, we report as eries of unprecedented giant highnuclearity heterometallic PONbs {Ln 12 12 ]·solv (1Ln,e n = ethylenediamine,s olv = solvents) that can be isolated as discrete inorganic sodium-potassium salts,a s shown by isolation of aY -based PONb Na 8 Figure S1), forming ac losed cage.T he free diameter of the largest sphere that can fit into the cage is approximately 0.7 nm (after consideration of the van der Waals radii of Eu and W). In the cage,s ome disordered water molecules are found to serve as the pore-filling species (Supporting Information, Figure S1).…”