Reductive Electron Transfer Quenching of MLCT Excited States Bound To Nanostructured Metal Oxide Thin Films

The ruthenium compounds Ru(deeb)(bpz)2(PF6)2, Ru(deeb)2(bpz)(PF6)2, and Ru(deeb)2(dpp)(PF6)2, where deeb is 4,4‘-(CO2CH2CH3)2-2,2‘-bipyridine, bpz is 2,2‘-bipyrazine, and dpp is 2,3-bis(2-pyridyl)pyrazine, have been prepared, characterized, and anchored to mesoporous nanoparticle thin films comprised of the wide band gap semiconductor TiO2 or the insulator ZrO2. The metal-to-ligand charge-transfer (MLCT) excited states of these compounds are potent photooxidants (E°(RuII*/+) > +1.0 V vs SCE) with long lifetimes (τ > 1 μs) that efficiently oxidize iodide and phenothiazine with rate constants that approach the diffusion limit in acetonitrile. Photogalvanic cells based on the sensitized TiO2 materials yield photocurrent action spectra that agree well with the Ru(II) absorptance spectra. The photocurrent efficiency was very low, φ -4. Transient absorption data show that neither the excited nor the reduced state of the ruthenium compounds efficiently inject electrons into the TiO2 particles. The cage escape yields following excited-state electron transfer are approximately 2/3 lower in the mesoporous thin films than in fluid solution. Intermolecular energy transfer across the nanoparticle surfaces is manifest in a second-order component to the excited-state relaxation kinetics

Thin Film Actinometers for Transient Absorption Spectroscopy: Applications to Dye-Sensitized Solar Cells

The chromophores Ru(bpy)3(PF6)2 and Os(bpy)3(PF6)2 were immobilized within poly(methyl methacrylate) (PMMA) thin films on glass substrates for applications as actinometers for nanosecond flash photolysis. Transient absorption difference spectra of M(bpy)3(PF6)2 (M = Ru, Os), at ambient temperature and in an argon atmosphere, were the same when imbedded in PMMA films as in solution, within experimental error. Linear ranges of ΔA versus 532 nm pulsed laser energy where these actinometers were applicable were identified, up to 25 mJ/(cm2 pulse) for Ru(bpy)32+/PMMA and up to 5 mJ/(cm2 pulse) for Os(bpy)32+/PMMA. Laser energy measurements were used to estimate the difference between the excited- and ground-state extinction coefficients at 450 nm for Os(bpy)32+, Δε450nm, which is −7300 M-1 cm-1. The Ru(bpy)32+/PMMA actinometer was useful from 300 to ∼550 nm, while the Os(bpy)32+/PMMA actinometer extends the sensitivity to ∼700 nm. An application of these actinometers for dye-sensitized solar cells is described, wherein the quantum yield for electron injection from Ru(dcbH2)(bpy)22+*, where dcbH2 is 4,4‘-(CO2H)2-2,2‘-bipyridine, into mesoporous nanocrystalline (anatase) TiO2 thin films was quantified as a function of ionic strength

Pseudohalogens for Dye-Sensitized TiO₂ Photoelectrochemical Cells

In this paper, we report on the preparation and characterization of two pseudohalogen redox couples for dye-sensitized TiO2 photoelectrochemical cells. The equilibrium potentials of the (SeCN)2/SeCN- and (SCN)2/SCN- couples are respectively 0.19 and 0.43 V more positive than for the I3-/I- couple, providing the opportunity to determine the influence of the redox potential on the open circuit photovoltage. With the sensitizer cis-Ru(dcb)2(NCS)2 (N3), the incident photon-to-current conversion efficiency was 20% for the (SeCN)2/SeCN- couple and 4% for the (SCN)2/SCN- couple. Transient absorbance measurements showed that the quantum yield for electron injection is independent of the pseudohalogen redox couple and that the regeneration rates of the dye decrease in the order I- > SeCN- > SCN-. The effects of the redox potential on open circuit photovoltage were determined by independent measurement of the dependence of the sensitized TiO2 working electrode and the platinum counter electrode potentials on the cell voltage