Synthesis, Structure and Light-Harvesting Properties of Some New Transition-Metal Dithiocarbamates Involving Ferrocene

Nine new transition-metal dithiocarbamates involving ferrocene (Fc), namely, [M(FcCH(2)Bzdtc)2] (M= (1), Cu-11(2), Cd-11 (3), Hg-11 (4), Pd-11 (5), Pt-II (6) and Pb-11 (7); Bzdtc=Nbenzyl dithiocarbamate) and [M(FcCH(2)Bzdtc)(3)] (M = Co-11 (8) and UO2VI (9)), have been synthesised and characterised by micro analyses, IR spectroscopy, H-1 and C-13 NMR spectroscopy, and in three cases by singlecrystal X-ray analysis. The peak broadening in the H-1 spectrum of the copper complex indicates the paramagnetic behaviour of this compound. A squareplanar geometry around the nickel and copper complexes and distorted linear geometry around the mercury complex have been found. The latter geometry is attributed to the bulkiness of the methylferrocenyl and benzyl groups. The observed single quasi-reversible cyclic voltammograms for complexes 2, 8 and 9 indicate the stabilisation of a metal centre other than Fe in their characteristic oxidation state. These complexes have been used as a photosensitiser in dye-sensitised solar cells.