Efficient phenylmercury(ii) methylferrocenyldithiocarbamate functionalized dye-sensitized solar cells

Abstract

Two new heterobimetallic phenylmercury(II) dithiocarbamate complexes incorporating the ferrocenyl moiety (C₅H₅)Fe(C₅H₄) (Fc), namely PhHgS₂CN(CH₂Fc)CH₂C₅H₄N, (1) and PhHgS₂CN(CH₂Fc)CH₂C₄H₃O, (2) have been prepared and characterized by elemental analysis, UV-Vis, IR, ¹H and ¹³C NMR spectroscopies. The crystal structures of 1 and 2 showed a linear core at the Hg(II) centre of the molecule, bound by the sulfur atom of the dithiocarbamate ligand and carbon atom of the aromatic ring. Weak intermolecular Hg⋯S interactions form “head-to-tail” dimers in the cases of 1 and 2. The observed quasi-reversible cyclic voltammograms of the complexes have been corroborated by calculating gross natural electron population and gross natural electron spin population at each atom for the neutral as well its oxidized species obtained at density functional level (DFT) of theory, which suggests that the delocalization of electron spin population can affect the magnitude of ΔE_p. The electronic absorption bands of both the complexes were assigned with the help of time dependent density functional theory (TD-DFT) calculations. The light harvesting properties of both 1 and 2 in conjunction with our previously reported compound PhHgS₂CN(CH₂Fc)CH₂C₆H₅ (3) have been reported.