Synthesis of ternary sulfide nanomaterials using dithiocarbamate complexes as single source precursors

We report the use of cheap, readily accessible and easy to handle di-isobutyl-dithiocarbamate complexes, [M(S 2 CN i Bu 2 ) n ], as single source precursors (SSPs) to ternary sulfides of ironnickel, ironcopper and nickelcobalt. Varying decomposition temperature and precursor concentrations has a significant effect on both the phase and size of the nanomaterials, and in some instances meta-stable phases are accessible. Decomposition of [Fe(S 2 CN i Bu 2 ) 3 ]/[Ni(S 2 CN i Bu 2 ) 2 ] at ca. 210230 C affords metastable FeNi 2 S 4 (violarite) nanoparticles, while at higher temperatures the thermodynamic product (Fe,Ni) 9 S 8 (pentlandite) results. Addition of tetra-isobutyl-thiuram disulfide to the decomposition mixture can significantly affect the nature of the product at any particular temperature-concentration, being attributed to suppression of the intramolecular Fe( iii ) to Fe( ii ) reduction. Attempts to replicate this simple approach to ternary metal sulfides of ironindium and ironzinc were unsuccessful, mixtures of binary metal sulfides resulting. Oleylamine is non-innocent in these transformations, and we propose that SSP decomposition occurs via primarysecondary backbone amide-exchange with primary dithiocarbamate complexes, [M(S 2 CNHoleyl) n ], being the active decomposition precursors. Heating mixtures of dithiocarbamate complexes in oleylamine leads to the formation of nanoparticulate ternary metal sulfides, the physical nature and phase of which can be tailored depending upon the reaction conditions adopted.