Cyanoacrylic- and (1-cyanovinyl)phosphonic acid anchoring ligands for application in copper-based dye-sensitized solar cells

The syntheses and characterization of four new anchoring ligands (2-5) for copper(I) bis(diimine) dyes in dye-sensitized solar cells (DSCs) are reported. Ligands 2 and 3 contain a 6,6'-dimethyl-2,2'-bipyridine copper-binding unit, while 4 and 5 contain a 2,9-dimethyl-1,1'-phenanthroline unit; 2 and 4 contain cyanoacrylic acid anchoring units, and 3 and 5 possess (1-cyanovinyl) phosphonic acid anchors. The performance of DSCs sensitized by [Cu(L-anchor)(L-ancillary)](+) in which L-anchor is 2-5 and L-ancillary is either 6,6'-dimethyl-2,2'-bipyridine (6) or 6-trifluoromethyl-2,2'-bipyridine (7) are compared with those of DSCs containing the dyes [Cu(1)(6)]+ or [Cu(1)(7)]+ where anchoring ligand 1 is the previously reported and well-performing ((6,6'-dimethyl-[2,2'-bipyridine]-4,4'-diyl) bis(4,1-phenylene)) bis(phosphonic acid). Among dyes incorporating 2-5, the best performing dye contained anchor 3 (6,6'-Me(2)bpy/(1-cyanovinyl) phosphonic acid combination). The better performances of dyes containing the bpy-based 2 and 3 compared to the phen-based 4 and 5 are rationalized largely in terms of the greater flexibility of the bpy vs. phen unit, allowing dyes containing 2 and 3 to adopt a conformation that leads to better surface coverage on mesoporous TiO2. Replacing 1 by 3 leads to a small gain in the short-circuit current density (J(SC)), but dyes with anchor 1 (in place of 3) have enhanced open-circuit voltage (VOC). The results of electrochemical impedance spectroscopy (EIS) support the trends found from the J-V measurements. The EIS data for DSCs with dyes containing anchors 3 or 1 are compared; the latter has a higher recombination resistance and chemical capacitance although the former exhibits a lower transport resistance.