Positional isomerism makes a difference: phosphonic acid anchoring ligands with thienyl spacers in copper(i)-based...

With the aim of improving the photoconversion efficiencies of heteroleptic [Cu(Lanchor)(Lancillary)](+) dyes in n-type dye-sensitized solar cells (DSCs), the previously favoured anchor ((6,6'-dimethyl-[2,2'-bipyridine]-4,4'-diyl)bis(4,1-phenylene))bis(phosphonic acid) (1) has been replaced by analogues 2 and 3 containing 2-thienyl spacers between the 2,2'-bipyridine metal-binding domain and the phosphonic acid anchoring groups. The synthesis and characterization of 2 and 3 (2-thienyl spacer with phosphonic acid in the 5- and 4-positions, respectively) are reported. A stepwise, on-surface method was used to assemble [Cu(Lanchor)(Lancillary)](+) dyes onto FTO/TiO2 electrodes with Lanchor = 1, 2 or 3, and Lancillary = 6,6'-bis(trifluoromethyl)-2,2'-bipyridine (4), 6-trifluoromethyl-2,2'-bipyridine (5), 6,6'-dimethyl-2,2'-bipyridine (6), and 6-methyl-2,2'-bipyridine (7). Changing the solvent in the dye-bath from CH2Cl2 to acetone had only a small effect on the photoconversion efficiencies of [Cu(1)(4)](+), [Cu(1)(5)](+) and [Cu(1)(6)](+); the optimal dye in this series was [Cu(1)(5)](+). Comparable DSC performances were achieved by using either anchor 1 or 2, but there is improved electron injection if the phosphonic acid group is in the 4- rather than 5-position of the thienyl ring (i.e. anchor 3 is superior to 2). Similar open-circuit voltages (VOC) are achieved on going from 1 to 3 with a given Lancillary; although there is typically a gain in short-circuit current denisty (JSC) on going from 1 or 3 to 2, there is an ≈50-60 mV drop in VOC on introducing 2 as the anchor. The best photoconversion efficiencies are obtained for the dye [Cu(3)(5)](+) (η = 2.40% relative to an N719 reference of 5.76%). The conclusions reached from plots of current-density (J) against potential (V), and external quantum efficiency spectra are supported by electrochemical impedance spectroscopic measurements.