Synthesis, structure and light-harvesting properties of some new transition-metal dithiocarbamates involving ferrocene

Nine new transition-metal di-thiocarbamates involving ferrocene (Fc), namely, [M(FcCH2Bzdtc)2] (M = NiII(1), Cu II (2), CdII (3), HgII (4), PdII (5), PtII (6) and PbII (7); Bzdtc = N-benzyl dithiocarbamate) and [M(FcCH2BZdtc)3] (M = CoII (8) and UO2 (9)), have been synthesised and characterised by micro analyses, IR spectroscopy, 1H and 13C NMR spec-troscopy, and in three cases by single-crystal X-ray analysis. The peak broad-ening in the 1H spectrum of the copper complex indicates the paramagnetic be-haviour of this compound. A square-planar 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 photo-sensitiser in dye-sensitised solar cells. 2010 Wiley-VCH Verlag GmbH Co. KGaA dithiocarbamates, fer-rocene, heterometallic complexes, solar cells, transition metals.