Heterocyclic Bismuth(III) Dithiocarbamato Complexes as Single‐Source Precursors for the Synthesis of Anisotropic Bi₂S₃ Nanoparticles

Abstract

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 Bi(III) ion are 8 for 1 and ≥6 for 2 when the experimental electron density for the nominal 6s(2) 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 Bi2 S3 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 Bi2 S3 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 Bi2 S3 .

Synthesis of (Bi1−xSbx)2S3solid solutionsviathermal decomposition of bismuth and antimony piperidinedithiocarbamates

“…The synthesis of (1) followed previously reported procedure with modications. 39 In a typical synthesis, carbon disulde (0.1 mol, 6.0 mL) was added to an equimolar mixture of sodium hydroxide (0.1 mol, 4.0 g) and piperidine (0.1 mol, 9.9 mL) cooled to 0 C. Aer Preparation of tris(piperidindithiocarbamato)bismuth(III) (2). The synthesis of (2) followed our previous procedure with modications.…”

“…38 In our earlier work, we showed that addition of a small amount of dodecanethiol was efficient in directing the shapes of Bi 2 S 3 rods from single source precursors by thermal decomposition of bismuth dithiocarbamate complexes in high boiling point coordination solvents. 39 This paper examines the effect of substituting antimony for bismuth on the structure of the bismuthinite-stibnite solid solution prepared by bismuth piperidine and antimony piperidine dithiocarbamate complexes.…”

Nickel Complexes Bearing SNN and SS Donor Atom Ligands: Synthesis, Structural Characterization and Biological activity

“…Generally, studies on related 2‐formylpyridine TSCs revealed the occurrence of thiol‐thione tautomerism in solution, and their monobasic tridentate nature [16] as these ligands bind metals through pyridyl (N), azomethine (N) and thiolate (S) atoms. On the other hand, DTCs coordinate the metals through their two sulfur atoms by forming four‐membered chelate rings . Preparation of the metal complexes is illustrated in Figure .…”

“…Apart from the TSCs, dithiocarbamates (DTCs) are bidentate SS ligands that have shown a broad spectrum of usefulness; they were employed as precursors to fabricate metal sulfide nanoparticles and for separation and quantification of metals . Biologically, DTCs were utilized to remove copper excesses that causes Wilson's disease, to treat alcoholism, as anti‐HIV and anticancer agents, which in certain cases displayed higher activity and lower toxicity in comparison to common anticancer drugs including cisplatin …”

Electrochemistry of Inorganic OCT-PbS/HDA and OCT-PbS Photosensitizers Thermalized from Bis(N-diisopropyl-N-octyldithiocarbamato) Pb(II) Molecular Precursors

“…The interesting chemical properties obtained from the use of dithiocarbamate complexes account for their applications in various fields. In addition to their wide application in the realm of materials science, they offer different arrays of anisotropic and isotropic nanomaterials [19][20][21]. In addition to their wide application, dithiocarbamate complexes offer a clean, nanometric dimension with no impurities when they undergo thermal decomposition [22].…”