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

The formation of mixed‐metal sulfides with the general structure AgBiS 2 and Cu 3 BiS 2 by a simple two‐step process utilizing bismuth dithiocarboxylates as Bi and S precursors is described. A sonochemical reaction of Bi 2 O 3 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 ⋅C 7 H 8 ] ( 3 2 ⋅C 7 H 8 ), [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 AgNO 3 or CuCl under mild reaction conditions (140 °C) resulted in the respective mixed‐metal sulfides. Attempt to synthesize AuBiS 2 using similar reaction protocols were unsuccessful, resulting only in the formation of elemental Au 0 , S 8 and BiOCl.