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Access to asymmetrically functionalized polyoxometalates is a grand challenge as it could lead to new molecular nanomaterials with multiple or modular functionality. Now, a simple one‐pot synthetic approach to the isolation of an asymmetrically functionalized organic–inorganic hybrid Wells–Dawson polyoxometalate in good yield is presented. The cluster bears two organophosphonate moieties with contrasting physical properties: a chelating metal‐binding group, and a long aliphatic chain that facilitates solvent‐dependent self‐assembly into soft nanostructures. The orthogonal properties of the modular system are effectively demonstrated by controlled assembly of POM‐based redox‐active nanoparticles. This simple, high‐yielding synthetic method is a promising new approach to the preparation of multi‐functional hybrid metal oxide clusters, supermolecular systems, and soft‐nanomaterials.  相似文献   

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The in situ formation of functionalized silica nanoparticles is reported. The reactive stabilizers used in the study, [3‐(2‐bromoisobutyryl)propyl]triethoxysilane and [3‐(2‐bromoisobutyryl)propyl]ethoxydimethylsilane, have an atom transfer radical polymerization (ATRP) initiator at the noncondensable end. Condensation with tetraethoxysilane yields silica nanoparticles with a surface‐immobilized initiator. The size of these functionalized silica nanoparticles can be controlled by varying the time of initiator addition and initiator concentration. The silica particle sizes ranged from 10 to 300 nm. With the initiator functionalized silica nanoparticles, ATRP synthesis was performed with styrene, tert‐butyl acrylate, and methyl acrylate to produce organic–inorganic nanomaterials.

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