This Review describes recent results on the precise spatial distribution control of metal and semiconductor nanoparticles into domains of microphase-separated block copolymers. Specific focus is directed towards selective incorporation into a specific microphase of a block copolymer. Details on theoretical aspects concerning nanoparticle incorporation as well as practical examples are given. Furthermore, examples on applications and technological aspects of the resulting nanoparticle/polymer nanocomposites are provided.

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The dealkylation of sulfonium salts with nucleophiles such as halide ions takes place effectively to yield poly(phenylene sulfide). The kinetic analysis by means of UV−vis spectroscopy reveals that the dealkylation proceeds quantitatively to convert the sulfonium bond to a thioether bond. The reaction rate constants of the dealkylation by the halide ions are in the order I- > Br- > Cl-. A propyl substituent on the sulfonium salt results in a lower dealkylation rate than that with methyl substituents, because of the steric hindrance of the propyl group. The demethylation of poly[methyl-(4-(phenylthio)phenyl)sulfonium trifluoromethanesulfonate] also proceeds efficiently on soaking thin films in dichloromethane solution containing tetraethylammonium halide for 20 h and results in the formation of a transparent and amorphous poly(p-phenylene sulfide) (PPS) film, because the synthetic procedure occurs under the glass transition temperature of PPS (90 °C), although PPS is well-known to be a highly crystalline polymer.

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The selective degradation of polyarylene sulfide via soluble polysulfonium salts was employed to give the monomer.

The electrochemistry of a l-oxo dimanganese(III) octaethylporphyrin (II) and those of the corresponding mononuclear complexes MnIII(OEP)Cl (I), (III) and MnIII(OEP)OH (IV) (where OEP MnIII(OEP)ClO 4 represents octaethylporphyrin) were studied. When complex II was adsorbed on an electrode and placed in aqueous acidic electrolyte solutions, efficient catalysis of the four-electron reduction of to was O 2 H 2 O accomplished. A control experiment using an electrode modiÐed with the mononuclear manganese(III) complex I resulted in a signiÐcant decrease in the selectivity for the four-electron reduction. The hydroxomanganese(III) complex IV was produced in the course of the oxidation of MnII(OEP) to MnIII(OEP)`with under acidic O 2 conditions. Complex I was isolated as single crystals and characterized by X-ray crystallography. Although complex II was not isolated as single crystals, the long manganese-axial ligand distance (2.385 in I provided Ó) an estimate that a similar geometry would be true for II, allowing accommodation of an molecule between O 2 the two manganese atoms in the adsorbed cofacial porphyrins.

The crystal structure of a μ-oxo heterometallic porphyrin [(pip)(tpp)CrIIIOFeIII(tpp)] (pip = piperidine) not only confirmed the proposed oxidation state of chromium and iron atoms, but also revealed a unique coordination environment around chromium(III), which is substantially protruded from the porphyrin plane.