Abstract
The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid‐state materials. Here, we report that functionalization of polyoxotungstates with organo‐boron substituents leads to giant polyoxometalate‐based nanocapsules with dimensions of up to 4 nm. A “lock and key” mechanism enables the site‐specific anchoring of aromatic organo‐boronic acids to metal‐functionalized Dawson anions [M3P2W15O62]9− (M=TaV or NbV), resulting in unique nanocapsules containing up to twelve POM units. Experimental and theoretical studies provide initial insights into the role of the organo‐boron moieties and the metal‐functionalized POMs for the assembly of the giant aggregates. The study therefore lays the foundations for the design of organo‐POM‐based functional nanostructures.
Highlights
The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid-state materials
Ence.[4À6] POMs are ideal prototypes for aggregation into larger nanostructures,[7,8,9] as a number of POM-linkage concepts have been established: currently, the field is dominated by the linkage of POMs using metal cation connectors.[10]. This concept has been most often used in polyoxotungstate chemistry, where Keggin- and Dawson-anions and their derivatives have been linked into giant cluster-of-cluster aggregates[11,12,13,14,15] or even polyoxometalate-based open frameworks.[2,16]
Cronin and colleagues used Dawson-polyoxotungstates functionalized with organic primary ammonium groups to aggregate tetrahedral nanostructures based on four Dawson anions using multiple hydrogen bonds between the organo-ammonium groups and the cluster oxide surface
Summary
The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid-state materials. Cronin and colleagues used Dawson-polyoxotungstates functionalized with organic primary ammonium groups to aggregate tetrahedral nanostructures based on four Dawson anions using multiple hydrogen bonds between the organo-ammonium groups and the cluster oxide surface.
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