Formation of Group 11 Bismuth Sulfide Nanoparticles Using Bismuth Dithioates under Mild Conditions.

The formation of mixed-metal sulfides with the general structure AgBiS2 and Cu3 BiS2 by a simple two-step process utilizing bismuth dithiocarboxylates as Bi and S precursors is described. A sonochemical reaction of Bi2 O3 with six different aryl dithioic acids: dithiobenzoic acid (BDT-H), 4-methoxydithiobenzoic acid (4-MBDT-H), 3-methyldithiobenzoic acid (3-MBDT-H), 2-mesitylenedithioic acid (2-MDT-H), 4-fluorodithiobenzoic acid (4-FBDT-H), and 2-thiophenedithioic acid (2-TDT-H) resulted in the corresponding complexes: [Bi(BDT)3 ] 1, [Bi(4-MBDT)3 ] 2, [{Bi(3-MBDT)3 }2 ⋅C7 H8 ] (32 ⋅C7 H8 ), [Bi(2-MDT)3 ] 4, [Bi(4-FBDT)3 ] 5 and [Bi(2-TDT)3 ] 6. Microwave irradiation of these bismuth(III)aryldithioate complexes with AgNO3 or CuCl under mild reaction conditions (140 °C) resulted in the respective mixed-metal sulfides. Attempt to synthesize AuBiS2 using similar reaction protocols were unsuccessful, resulting only in the formation of elemental Au0 , S8 and BiOCl.