Synthesis of new low band gap dyes with BF2–azopyrrole complex and their use for dye-sensitized solar cells

The diazonium salt derived from 4-aminobenzoic acid, 4-aminophenol or 2-aminophenol reacted with half equivalent of pyrrole to afford symmetrical 2,5-bisazopyrroles. They reacted subsequently with boron trifluoride in the presence of triethylamine to afford the corresponding BF2–azopyrrole complexes D1, D2 and D3 respectively. They were soluble and stable in nonprotic solvents such as chloroform, dichloromethane and tetrahydrofuran but unstable in protic solvents such as ethanol. Their absorption spectra were broad with optical band gap of 1.49–1.70 eV. Among these dyes D2 displayed the broader absorption spectrum with low band gap Egopt of 1.49 eV. We have utilized these complexes as photosensitizers for quasi solid state dye-sensitized solar cells (DSSCs) and achieved power conversion efficiency in the range of 4.0–6.0%. We have also found that the co-adsorption of citric acid hindered the formation of dye aggregates and might improve the electron injection efficiency leading to an enhancement in short circuit photocurrent. This work suggests that metal-free dyes based on BF2–azopyrrole complex are promising candidates for improvement of the DSSC performance.