Copper(I) and gold(I) thiolate precursors to bimetallic nanoparticles

Abstract Copper(I) and gold(I) thiolates were synthesized in quantitative or near-quantitative yield by the direct reaction of aqueous Cu(NO 3 ) 2 or HAuCl 4 with aqueous thiols HSCH 2 CH 2 OH and HSCH 2 CH 2 OCH 2 CH 2 OH. The resulting highly insoluble thiolates had spectroscopic and bulk characteristics consistent with the formation of coordination polymers of general formula [M(SR)] n . The gold(I) thiolates were found to be amorphous solids with significant aurophilic interactions. The copper(I) thiolates, however, formed crystalline solids without discernible cuprophilic interactions. Characterization of the solid state structure of these latter thiolates showed that they consisted of covalently linked ca. two-atom thick Cu–S layers separated by layers of hydrogen bonded thiol side chains.