Organic dyes containing fluorenylidene functionalized phenothiazine donors as sensitizers for dye sensitized solar cells

Two new organic sensitizers featuring fluorenylidene decoration on the phenothiazine donor have been synthesized and characterized as sensitizers for nanocrystalline TiO₂-based dye sensitized solar cells (DSSCs). The dyes possess cyanoacrylic acid as acceptor/anchoring group and a conjugation pathway composed of fluorene and thiophene. Introduction of the fluorenylidene moiety on phenothiazine enhances the optical density of the dyes while the extension of conjugation by thiophene insertion red-shifts the absorption peak originating from the intramolecular charge transfer from phenothiazine to cyanoacrylic acid. The ground and excited state oxidation potentials of the fluorenylidene-containing dyes are upwardly shifted when compared to the parent dyes indicating a π-delocalized donor segment. The electronic properties were supported by density functional theoretical computations. Among the DSSCs fabricated, the dye (5a) having fluorene and thiophene in the spacer resulted higher power conversion efficiency (3.31 %) than the corresponding bithiophene analog (5b, 2.83 %) attributable to the relatively high electron life time and enhanced resistance for recombination in the former.