Articles written in Journal of Chemical Sciences
Volume 105 Issue 6 October 1993 pp 539-554
We have studied transmembrane electron transfer mediated by an amphiphilic viologen (C16,1′ V2+) in lecithin vesicles. There is no long-range electron transfer between viologens bound to opposite interfaces of the vesicle membrane, as is often proposed. Instead we proposed a mechanism where the rate-determining step is the disproportionation of two viologen radical cations (2C16,1′ V+ ⇔C16,1′ V2+ + C16,1′ V0) forming a doubly reduced, uncharged viologen that transfers electrons by rapid transmembrane diffusion and subsequent reduction of electron acceptors. Studies on other redox mediators provided further information. A brief background to the field is given, including comments on work done by others in relevant systems.
Volume 109 Issue 6 December 1997 pp 389-396 Photochemical Conversion And Storage Of Solar Energy
One attractive way to harvest solar energy is to use the concepts of natural photosynthesis in an artificial system. In green plant photosynthesis, the solar energy is transformed into usable energy in the form of reduced compounds. The electrons come from water which is oxidized to molecular oxygen, thereby providing the plants with a never ending supply of reducing equivalents. In photosystem II, the photosensitizer is a chlorophyll species, P680, which is coupled to a cluster composed of four manganese ions that catalyses the water oxidation. We have tried to mimic this by the synthesis of a binuclear compound [Ru(bpy)2(Mebpy-Mebpy)MnCl2(H2O)2]Cl2 built on bipyridine ligands containing a Ru(II) moiety (the photosensitizer) and a Mn(II) ion (the donor) linked via a bridging ligand. In the complex, which is structurally defined by NMR, elemental analysis and electrospray mass spectroscopy, we have observed, (1) the Mn is sufficiently close (about 13Å) to interact with the Ru(II) ion, and (2) intramolecular, photochemically induced electron transfer from Mn(II) to the photogenerated Ru(III) moiety after a light flash in the presence of an electron acceptor. We suggest that the synthesis, characterization and observation of intramolecular electron transfer in this novel Ru-Mn compound is an important step towards artificial photosynthesis.
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