Although considerable effort has been dedicated to the controlled synthesis of nanoparticles with classical inorganic structures, there are few reports on the formation of nanoscale materials based on supramolecular compounds such as transition metal coordination polymers. Here we describe the synthesis of crystalline nanoparticles of three different molecule-based magnetic materials, cobalt hexacyanoferrate, cobalt pentacyanonitrosylferrate, and chromium hexacyanochromate, by coprecipitation reactions involving mixtures of water-in-oil microemulsions. The cobalt-containing nanoparticles are regular in shape and size and have dimensions between 12 and 22 nm depending on the concentration of the reactants trapped within the water droplets. At sufficiently high particle concentrations, superlattice structures are formed by solvent evaporation. Growth of the nanoparticles occurs by interdroplet aggregation of primary clusters that are nucleated in the confined spaces of the microemulsion reaction field.

Triadic photoanodes have been prepared based on nanoporous films of the metal oxides ZrO2, TiO2 and SnO2, sensitizer [Ru(bpy)2(dpbpy)] 2+ (P2) and polyoxometalate water oxidation catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2] 10-(1), and investigated for their potential utility in water-splitting dye-sensitized photoelectrochemical cells. Transient visible and mid-IR absorption spectroscopic studies were carried out to investigate the charge separation dynamics of these systems, indicating that the electron transfer from photoexcited P2 to TiO2 and SnO2 is still the main excited state quenching pathway in the presence of 1. Furthermore, the accelerated recovery of the P2 ground state bleach in the presence of 1 results from ultrafast (nanosecond) electron transfer from catalyst to oxidized dye. Catalyst loading appears to depend largely on the point of zero charge of the supporting oxide and as such is significantly lower on SnO2 than on TiO2: nonetheless, the rate of recovery of the ground state bleach is similar in both TiO2-P2-1 and SnO2-P2-1 films. Spectral evidence for the formation of long-lived charged separated states is provided by the observation of signals persisting beyond 0.5 μs which are attributed to Stark effect induced change of the P2 spectrum and/or formation of oxidized 1. Photoelectrochemical measurements on TiO2-P2 and TiO2-P2-1 photoanodes under visible light irradiation indicate a ca. 100% photocurrent enhancement in the presence of 1, suggesting light-driven water oxidation by the TiO2-P2-1 system with an internal quantum efficiency of ca. 0.2%. The fast formation and long lifetime of the photo-oxidized catalyst sug-