Corrosiveness is one of the main drawbacks of using the iodide/triiodide redox couple in dye-sensitized solar cells (DSSCs). Alternative redox couples including transition metal complexes have been investigated where surprisingly high efficiencies for the conversion of solar to electrical energy have been achieved. In this paper, we examined the development of a DSSC using an electrolyte based on square pyramidal oxidovanadium(IV/V) complexes. The oxidovanadium(IV) complex (Ph4P)2[V(IV)O(hybeb)] was combined with its oxidized analogue (Ph4P)[V(V)O(hybeb)] {where hybeb(4-) is the tetradentate diamidodiphenolate ligand [1-(2-hydroxybenzamido)-2-(2-pyridinecarboxamido)benzenato}and applied as a redox couple in the electrolyte of DSSCs. The complexes exhibit large electron exchange and transfer rates, which are evident from electron paramagnetic resonance spectroscopy and electrochemistry, rendering the oxidovanadium(IV/V) compounds suitable for redox mediators in DSSCs. The very large self-exchange rate constant offered an insight into the mechanism of the exchange reaction most likely mediated through an outer-sphere exchange mechanism. The [V(IV)O(hybeb)](2-)/[V(V)O(hybeb)](-) redox potential and the energy of highest occupied molecular orbital (HOMO) of the sensitizing dye N719 and the HOMO of [V(IV)O(hybeb)](2-) were calculated by means of density functional theory electronic structure calculation methods. The complexes were applied as a new redox mediator in DSSCs, while the cell performance was studied in terms of the concentration of the reduced and oxidized form of the complexes. These studies were performed with the commercial Ru-based sensitizer N719 absorbed on a TiO2 semiconducting film in the DSSC. Maximum energy conversion efficiencies of 2% at simulated solar light (AM 1.5; 1000 W m(-2)) with an open circuit voltage of 660 mV, a short-circuit current of 5.2 mA cm(-2), and a fill factor of 0.58 were recorded without the presence of any additives in the electrolyte.
Reaction of an aqueous solution of NaVO3 or a methanol solution of [VO(acac)2] with 2,5-bis((bis(2-hydroxyethyl)amino)methyl)hydroquinone, H6bdeah, results in the formation of two major vanadium species characterized by X-ray crystallography: the [(V(5+)O)2(bdeah)] and the [(V(4.5+)O)2(bdeas)S2] (S = DMSO or MeOH). The vanadium ions in the two species have a trigonal pyramidal and an octahedral coordination sphere respectively. Variable temperature UV-Vis and (51)V NMR spectroscopy as well as EPR and electrochemistry showed a temperature induced electron transfer. The diamagnetic [(V(5+)O)2(bdeah)] is the main species at high temperature. At low temperature one electron is transferred from the bdeah(6-) to the two vanadium centers resulting in the [(V(4.5+)O)2(bdeas)S2] species [H5bdeas = 2,5-bis((bis(2-hydroxyethyl)amino)methyl)-1,4-semiquinone]. The thermodynamic parameters of this intramolecular electron transfer were calculated by UV-Vis (ΔH = -36 ± 2 kJ mol(-1) and ΔS = -129 ± 5 J mol(-1) K(-1)) and (51)V NMR spectroscopy (ΔH = -37 ± 2 kJ mol(-1) and ΔS = -109 ± 5 J mol(-1) K(-1)). The electron transfer is a result of the large change of entropy which is associated with the ligation of the solvent molecules and the geometry change. EPR spectroscopy shows that most of the electron density in [(V(4.5+)O)2(bdeas)S2] is mainly located on the two vanadium ions.
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