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 our findings on the macromolecule-to-amphiphile conversion process of a polyoxometalate-polymer hybrid and the assembled hybrid vesicles formed by aggregation of the hybrid amphiphile. The polyoxometalate-polymer hybrid is composed of a polyoxometalate (POM) cluster, which is covered by five tetrabutylammonium (Bu(4)N(+)) countercations, and a polystyrene (PS) chain. Through a cation-exchange process the Bu(4)N(+) countercations can be replaced by protons to form a hybrid amphiphile composed of a hydrophilic, protonated POM cluster and a hydrophobic PS chain. By implementing a directed one-dimensional diffusion and analyzing the diffusion data, we confirmed that the diffusion of solvated protons rather than macromolecules or aggregates is the key factor controlling the conversion process. Once the giant hybrid amphiphiles were formed, they immediately assembled into kinetically favored vesicular aggregates. During subsequent annealing these vesicular aggregates were transformed into thermodynamically stable vesicular aggregates with a perfect vesicle structure. The success in the preparation of the POM-containing hybrid vesicles provides us with an opportunity of preparing POM-functionalized vesicles.

The originally synthesized hydrophobic hybrid polymer Bu4N+‐POM‐PS is tuned into a giant amphiphile composed of a hydrophilic H+‐POM head and a hydrophobic PS tail through protonation. Immediately, the hybrid amphiphiles self‐assemble into vesicles. A further annealing treatment induces an evolution from vesicles to tubular aggregates containing H+‐POM nanotubes wrapped with PS coronas. After this transformation, the tubular aggregates grow further and then arrange in a parallel manner to form domains. This interesting morphology evolution provides us an opportunity to understand the intriguing aggregation behavior of the hybrid amphiphiles and, meanwhile, to generate POM nanotubes which might be utilized to create nanomaterials for potential applications.

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