Three monoanionic dithio compounds viz. potassium N-benzyl-N-methylferrocenyl dithiocarbamate (1), potassium ferrocenyl imino ethyl-2-dithiocarbonate (2) and potassium N-2-hydroxy-ethyl-N-methylferrocenyl dithiocarbamate (3) have been synthesized and characterized by elemental analyses, IR, UV-Vis, H-1 and C-13 NMR spectroscopy. For the first time the light harvesting properties of these types of compounds with sulphur as an anchoring group have been investigated. The solar-cell performances of DSSCs based on dye-grafted nanocyrstalline TiO2 using 1-3 and standard N3 (bis[(4,4'-carboxy-2,2'-bipyridine)(thiocyanato)ruthenium(III)]) are compared, revealing substantial dependences on the dye structure. The cyclic voltammograms of the dyes have been explained using DFT calculations and the electron injection has been explained using density of states (DOS) plot for (TiO2)(30) + 1 system. Electrochemical impedance spectroscopy has been performed to measure the charge-transfer resistance for TiO2/dye/electrolyte interface system and to corroborate the efficiency obtained from the dye-grafted solar cells. The 1-based device show the best performance: eta = 5.39 +/- 0.03%, J(sc) = 10.70 +/- 0.06 mA cm(-2), V-oc = 0.697 +/- 0.004 V and FF = 0.71 +/- 1. Long term stability of the photocurrent output of the cell using dye 1 as photosensitizer has been monitored during 1000 h. (C) 2014 Elsevier Ltd. All rights reserved.