Nanothallium(III) sulphide from dithiocarbamate precursors: synthesis, single crystal X-ray structures and characterization

Nanothallium sulfide was formed from Tl(chmdtc)3(1), Tl(chedtc)3(2) and Tl(dchdtc)3(3) (where chmdtc = cyclohexyl methyl dithiocarbamate, chedtc = cyclohexylethyl dithiocarbamate, dchdtc = dicyclohexyl dithiocarbamate). Single crystal structures of the complexes are reported. The ease of formation was the highest for (3) and is in line with the longest mean Tl–S and thioureide C–N bonds observed for (3). The nano metal sulfide formed is spherical in nature and has been characterized by PXRD, EDX, TEM. Tl4S3 was stable up to 300 °C. Thioureide stretching bands are observed at 1471, 1468, 1448 cm−1 for (1), (2) and (3) respectively. Thioureide stretching band of (3) is significantly lower than others due to steric effect of cyclohexyl substituents. Thallium(III) complexes exhibit fully allowed charge transfer transitions(CT) which appeared as intense absorptions. 1H NMR shows that the α-CH and α′-CH3 protons are affected to a maximum effect on complexation. 13C NMR spectra show thioureide carbon signal around 200 ppm.