An organic-inorganic hybrid polymer composed of a Dawson trivanadium-substituted heteropolytungstate ((Bu 4 N) 5 [H 4 P 2 W 15 V 3 O 62 ]) cluster and PS chain are originally designed and first synthesized via in situ ATRP. Further characterization includes NMR spectroscopy, FT-IR spectroscopy, and GPC which proved the purity of the material. By means of a cation exchange process, a hybrid polymer (Bu 4 N) þ -POM-PS was tuned into a novel giant amphiphile H þ -POM-PS. Immediately, individual molecules self-assembled into kinetically favored hybrid vesicles in DMF. Our work provides a controllable and rational way to fabricate stable and well-defined POM-polymer hybrid polymers that can be optimized for potential applications.

We report the construction of dumbbell-shaped hybrid molecules for programming their hierarchical supramolecular nanostructures through a synergetic self-assembly. Our first dumbbell-shaped hybrid molecule is a POM-organic-POSS cocluster produced by covalently coupling a POM cluster and a POSS cluster together through an organic tether. Structural analyses demonstrated a highly ordered lamellar morphology with a 4.9 nm periodicity, indicating a strong thermodynamic force driving a nanoscale phase separation of the POM and POSS blocks. The POM clusters were arranged in an orderly fashion within the POM-containing layer with a 1.38 nm periodicity because of fixed shape and size of the cluster. This investigation provides in-depth understanding of how to construct hierarchical supramolecular nanostructures at a nanoscale less than 5 nm by manipulating and controlling the topological shape of hybrid molecules.

Organic polymers have been found widespread commercial applications due to their easy processing and attractive mechanical properties. Concurrently, inorganic polyoxometalates (POMs), a class of metal–oxygen anionic and nanosized clusters of early transition metals, have a wide range of attractive functions and are used in industrial catalysis. In this communication, we report a new approach to creating the first linear poly(polyoxometalate)s that combine the advantages of polymers and POM clusters. In the experiment, a POM-containing norbornene monomer was first synthesized by linking a Wells-Dawson-type POM with a norbornene derivative. The monomer was polymerized in the presence of a Grubbs catalyst under mild conditions with yields nearly 100% in a living and controllable manner. The resulting poly(polyoxometalate)s have controllable molecular weights and a well-defined hybrid structure of an organic polynorbornene backbone with large pendant groups of the nanosized POM clusters. Thus, they form good films and have a good catalytic performance. Our findings not only pave the way for incorporating the POM clusters into polymers with well-defined structures and high molecular weights, but also offer a competitive strategy for developing more novel catalytic systems by introducing the poly(polyoxometalate)s.

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