Journal of Physical Chemistry B, Vol.104, No.9, 2099-2108, 2000
Vectorial multistep electron transfer at the gold electrodes modified with self-assembled monolayers of ferrocene-porphyrin-fullerene triads
Self-assembled monolayers of ferrocene-porphyrin-C-60 triads on gold electrodes were prepared to mimic photosynthetic electron transfer events where efficient conversion of light to chemical energy takes place via the long-lived, charge-separated state with a high quantum yield. Adsorbed amounts of the triads on the gold electrodes, estimated from the charge of the anodic peak of the ferrocene, are comparable to those of the well-ordered porphyrin-alkanethiols and C-60-alkanethiols on gold electrodes. The results, together with blocking experiments using a redox probe, indicate that the triad molecules are well-packed with an almost perpendicular orientation on the gold surface. The monolayer thickness obtained using X-ray reflectivity analysis is consistent with the structural model of the monolayer. Photoelectrochemical studies were carried out in a standard three-electrode system using the gold electrodes modified with the self-assembled monolayers of the triads. Stable cathodic photocurrents were observed in the presence of electron carriers such as oxygen and/or methyl viologen in the electrolyte when the modified gold electrodes were illuminated with a monochromic Light. A photoinduced multistep electron-transfer mechanism is proposed for the photoelectrochemical cells. Thus, vectorial electron transfer or partial charge transfer occurs from the excited singlet state of the porphyrin to the C-60, followed by the successive charge shift from the ferrocene to the porphyrin cation radical, to produce the ferrocene cation radical and the C-60 anion radical. The C-60 anion radical gives an electron to the counter electrode via the electron carriers in the electrolyte solution, whereas electron transfer takes-place from the gold electrode to the ferrocene cation radical, resulting in the recovery of the initial state and the generation of the overall electron flow. The artificial photosynthetic cells show the highest quantum efficiency (20-25%) ever reported for photoinduced multistep electron transfer at monolayer-modified metal electrodes and across artificial membranes using donor-acceptor linked molecules. The result indicates clearly that C-60 acts as an excellent electron acceptor as well as an electron mediator in artificial photosynthetic membranes. The molecule-based methodology will provide a new direction for the development of solar energy conversion and molecular devices.
Keywords:PHOTOINDUCED CHARGE SEPARATION;LANGMUIR-BLODGETT MONOLAYERS;TIME-RESOLVED FLUORESCENCE;MODIFIED SNO2 ELECTRODES;INTRAMOLECULAR ELECTRON;PHOTOPHYSICAL BEHAVIOR;PHOTOELECTRICCONVERSION;MOLECULAR-ORGANIZATION;ALKANETHIOL MONOLAYERS;SURFACTANT PORPHYRINS