Intramolecular Electron Transfer from Manganese(II) Coordinatively Linked to a Photogenerated Ru(III)-Polypyridine Complex: A Kinetic Analysis

For further investigations in the field of artificial photosynthesis, a model compound, 1, has been developed to mimic the electron-transfer steps from the manganese cluster to P680+ in photosystem II. In this model compound the photosensitizer ruthenium(II)-trisbipyridyl was linked to a manganese(II) ion through a bridging ligand. Photoexcitation of 1 in the presence of the electron acceptor methyl viologen (MV2+) lead to electron transfer from the Ru moiety to MV2+. Laser flash photolysis experiments at different concentrations of 1 were performed in order to follow the subsequent reduction of the photooxidized Ru(III) species. A kinetic model, taking different parallel reactions into account, could explain the experimental data. It was shown that the major part of the photooxidized Ru(III) created was reduced again by intramolecular electron transfer from the attached Mn(II), with a rate constant of 1.8 × 105 s-1. However, Mn(II) was partially dissociated from 1, giving a fraction of Ru(III) without Mn(II) attached. In these complexes electron transfer could occur only after a rate-limiting reassociation of Mn(II), with a rate constant 2.9 × 109 M-1 s-1. In the analysis of the data, the fraction of dissociated Mn(II) could be determined independently at each concentration of 1, utilizing the fact that bound Mn(II) quenched the excited state, probably by energy transfer.