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Linear triads with ruthenium photosensitizers are frequently based on the Ru(terpyridine)(2)(2+) unit. We report on vectorial photoinduced electron transfer in a linear triad based on the Ru(bipyridine)(3)(2+) photosensitizer. Electron-hole separation over a 22 Å-distance is established with a quantum yield greater than 64% and persists for 1.3 μs in acetonitrile.

We report on the synthesis of organized arrays of gold (Au) nanoparticles on thermally oxidized Si wafers using sputtering as a metal deposition method in combination with sphere lithography. This simple process leads to the formation of a honeycomb mask of Au at room temperature (RT). We study the transformation mechanism of this honeycomb mask to a hexagonal array of Au nanoparticles by annealing at different temperatures and in different atmospheres. The underlying mechanisms of pattern formation during annealing are coalescence of particles and Ostwald ripening and depend on temperature and atmosphere. The crystallinity and orientation of the nanoparticles with respect to the underlying substrate is analyzed by electron backscatter diffraction (EBSD), and the control of the morphology, size, shape, and orientation in different atmospheres (argon (Ar), nitrogen (N2), air, hydrogen (H2), and vacuum) is discussed.

Quinones play a key role as primary electron acceptors in natural photosynthesis, and their reduction is known to be facilitated by hydrogen-bond donors or protonation. In this study, the influence of hydrogen-bond donating solvents on the thermodynamics and kinetics of intramolecular electron transfer between Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) and 9,10-anthraquinone redox partners linked together via one up to three p-xylene units was investigated. Addition of relatively small amounts of hexafluoroisopropanol to dichloromethane solutions of these rigid rodlike donor-bridge-acceptor molecules is found to accelerate intramolecular Ru(bpy)(3)(2+)-to-anthraquinone electron transfer substantially because anthraquinone reduction occurs more easily in the presence of the strong hydrogen-bond donor. Similarly, the rates for intramolecular electron transfer are significantly higher in acetonitrile/water mixtures than in dry acetonitrile. In dichloromethane, an increase in the association constant between hexafluoroisopropanol and anthraquinone by more than 1 order of magnitude following quinone reduction points to a significant strengthening of the hydrogen bonds between the hydroxyl group of hexafluoroisopropanol and the anthraquinone carbonyl functions. The photoinduced intramolecular long-range electron transfer process thus appears to be followed by proton motion; hence the overall photoinduced reaction may be considered a variant of stepwise proton-coupled electron transfer (PCET) in which substantial proton density (rather than a full proton) is transferred after the electron transfer has occurred.