Photoactive Molecular Dyads [Ru(bpy)₃-M(ttpy)₂] ⁿ⁺ on Gold (M = Co(III), Zn(II)): Characterization, Intrawire...

We propose in this work a stepwise approach to construct photoelectrodes. This takes advantage of the self-assembly interactions between thiol with a gold surface and terpyridine ligands with first-row transition metals. Here, a [Ru(bpy)₃]²⁺ photosensitive center bearing a free terpyridine group has been used to construct two linear dyads on gold (Au/[Zn^II-Ru^II]⁴⁺ and Au/[Co^III-Ru^II]⁵⁺). The stepwise construction was characterized by electrochemistry, quartz crystal microbalance, and atomic force microscopy imaging. The results show that the dyads behave as rigid layers and are inhomogeneously distributed on the surface. The surface coverages are estimated to be in the order of 10^-11 mol cm^-2. The kinetics of the heterogeneous electron transfer is determined on modified gold ball microelectrodes using Laviron's formula. The oxidation rates of the terminal Ru(II) subunits are estimated to be 700 and 2300 s^-1 for Au/[Zn^II-Ru^II]⁴⁺ and Au/[Co^III-Ru^II]⁵⁺, respectively. In the latter case, the rate is limited by the kinetics of electron transfer between an intermediate Co(II) center and the gold surface. For Au/[Zn^II-Ru^II]⁴⁺, the Zn-bis-terpyridine center is not involved in the electron-transfer process and the oxidation of the Ru(II) subunit occurs through a superexchange process. In the presence of a tertiary amine in solution, the electrodes at a bias of 0.12 V behave as photoanodes when subjected to visible light irradiation. The magnitude of the photocurrent is around 10 μA cm^-2 for Au/[Co^III-Ru^II]⁵⁺ and 5 μA cm^-2 for Au/[Zn^II-Ru^II]⁴⁺, proving the importance of an electron relay on the photon-to-current conversion. The results suggest an efficient conversion for Au/[Co^III-Ru^II]⁵⁺, since each bound dyad, once excited, injects an electron around 10 times per second.