Heterocyclic Bismuth(III) Dithiocarbamato Complexes as Single-Source Precursors for the Synthesis of Anisotropic Bi2S3Nanoparticles

2016 
New complexes catena-(μ2-nitrato-O,O′)bis(piperidinedithiocarbamato)bismuth(III) (1) and tetrakis(μ-nitrato)tetrakis[bis(tetrahydroquinolinedithiocarbamato)bismuth(III)] (2) were synthesised and characterised by elemental analysis, FTIR spectroscopy and thermogravimetric analysis. The single-crystal X-ray structures of 1 and 2 were determined. The coordination numbers of the BiIII ion are 8 for 1 and ≥6 for 2 when the experimental electron density for the nominal 6s2 lone pair of electrons is included. Both complexes were used as single-source precursors for the synthesis of dodecylamine-, hexadecylamine-, oleylamine and tri-n-octylphosphine oxide-capped Bi2S3 nanoparticles at different temperatures. UV/Vis spectra showed a blueshift in the absorbance band edge characteristic of a quantum size effect. High-quality, crystalline, long and short Bi2S3 nanorods were obtained depending on the thermolysis temperature, which was varied from 190 to 270 °C. A general trend of increasing particle breadth with increasing reaction temperature and increasing length of the carbon chain of the amine (capping agent) was observed. Powder XRD patterns revealed the orthorhombic crystal structure of Bi2S3.
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