Monoorganobismuth(III) dithiocarboxylates: Synthesis, structures and their utility as molecular precursors for the preparation of Bi2S3 films and nanocrystals

Synthesis of a series of monoorganobismuth dithiocarboxylate complexes, [RBi(S2CAr)2] (R = Me, Ph, tol; Ar = Ph, tol), has been reported. They have been characterized by elemental analyses and spectroscopic methods. Molecular structures of [RBi(S2Ctol)2] (R = Me or Ph) have been established by single crystal X-ray diffraction studies. The bismuth atom in these complexes adopts a square pyramidal configuration with the R group at the apical position. In the solid state, these complexes show supra-molecular association devoid of Bi⋯S secondary interactions. Thermolysis of [RBi(S2Ctol)2] (R = Me or Ph) in refluxing diphenylether yielded Bi2S3 nanocrystals which were characterized by XRD, EDAX and SEM. The complex [PhBi(S2Ctol)2] has been employed for deposition of thin films of Bi2S3 by AACVD.