Stabilization of {Ag20(StBu)10} and {Ag19(StBu)10} Toroidal Complexes in DMSO: HPLC-ICP-AES, PL, and Structural Studies

Abstract

The presence of DMSO provides a unique ability to stabilize silver toroidal complexes in the direct reaction between AgStBu and AgNO3 at 80 °C. Slow cooling results in large crystals of [NO3@Ag19.2(StBu)10(DMSO)5.2(NO3)8.2]·3DMSO (1), which were isolated and characterized by single crystal X-ray diffraction (SCXRD) analysis. The crystal structure contains both {Ag20(StBu)10} and {Ag19(StBu)10} clusters. The solution of these material in DMSO was studied with HPLC techniques, which demonstrated the presence of both complexes in solution. The use of [SiW12O40]4– as counter anion gives crystals of a double complex salt [Ag17.8(NO3)3.8(StBu)10][SiW12O40]·30DMSO (2) under the same conditions. Temperature-dependent photoluminescence (PL) was studied.

Recent progress in dichalcophosphate coinage metal clusters and superatoms

“…14 An almost unlimited set of C-, P-, S-, Se-and Te-donating ligands, as well as their ability to modulate the structure of clusters and tune their properties, open up wide prospects for the design of the most fascinating cluster complexes. Up to now, a plethora of Cu, Ag and Au clusters supported by chalcogenide, [15][16][17][18] phosphine, 19,20 carbene, 21 alkynyl, 22,23 and polyoxometalate 24 anions were assembled. Other remarkable families of supporting ligands for stable group 11 metal clusters are dichalcophosphates ([(RO) 2 PE 2 ] À ) (E = S or Se), 25,26 which are readily available on a large scale from the cheapest starting reagents -P 2 S 5 or P 2 Se 5 and diverse alcohols.…”