Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices.

Block copolymer self-assembly in solution paves the way for the construction of well-defined compartmentalized nanostructures. These are excellent templates for the incorporation and stabilisation of nanoparticles (NPs), giving rise to highly relevant applications in the field of catalysis or sensing. However, the regio-selective incorporation of NPs in specific compartments is still an issue, especially concerning the loading with different NP types. Using crystallisation-driven self-assembly (CDSA), functional worm-like crystalline-core micelles (wCCMs) with a tailor-made, nanometre-sized patchy corona were prepared as versatile templates for the incorporation and stabilisation of metal and metal oxide NPs. Different strategies, like ligand exchange or co-precipitation of polymer stabilised NPs with one surface patch, were developed that allow the incorporation of NPs in specific regions of the patchy wCCM corona. Independent of the NP type and the incorporation method, the NPs showed no tendency for agglomeration and were fixed within the corona patches of the wCCMs. The binary loading of patchy micelles with metal and metal oxide NPs was realised by combining different loading strategies, yielding hybrids with homogeneously dispersed NPs guided by the patchy structure of the template.

Hexagonally ordered mesoporous molybdenum oxycarbide/carbon (MoC/C) nanocomposites were directly accessed by heat treatment of mesostructured poly(butadiene-block-2-vinylpyridine) (PB-b-P2VP) and molybdophosphoric acid. PB-b-P2VP serves as structure-directing agent and as carbon source. The high specific surface area obtained for the nanocomposites renders the materials interesting for potential applications, such as in the catalytic decomposition of NH3

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