A series of molecularly engineered and novel dyes WS1, WS2, WS3, and WS4, based on the D35 donor, 1-(4-hexylphenyl)-2,5-di(thiophen-2-yl)-1H-pyrrole and 4-(4-hexylphenyl)-4H-dithieno[3,2-b: 2', 3'-d] pyrrole as pi-conjugating linkers, were synthesized and compared to the well-known LEG4 dye. The performance of the dyes was investigated in combination with an electrolyte based on Co(II/III) complexes as redox shuttles. The electron recombination between the redox mediators in the electrolyte and the TiO2 interface decreases upon the introduction of 4-hexylybenzene entities on the 2,5-di(thiophen-2-yl)-1H-pyrrole and 4H-dithieno[3,2-b: 2', 3'-d] pyrrole linker units, probably because of steric hindrance. The open circuit photovoltage of WS1-, WS2-, WS3-, and WS4-based devices in combination with the Co(II/III)-based electrolyte are consistently higher than those based on a I-/I-3(-) electrolyte by 105, 147, 167, and 75 mV, respectively. The WS3-based devices show the highest power conversion efficiency of 7.4% at AM 1.5 G 100 mW/cm(2) illumination mainly attributable to the high open-circuit voltage (V-OC).
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