Silver(I) Sulfide Clusters Protected by Rhodium(III) Metalloligands with 3-Aminopropanethiolate.

The two homochiral Ag I Rh III nanoclusters, Δ 6 /Λ 6 -[Ag 11 S{Rh(apt) 3 } 6 ] 9+ ([ 1 ] 9+ ) and Δ 6 /Λ 6 -[Ag 13 S{Rh(apt) 3 } 6 ] 11+ ([ 2 ] 11+ ), in which Ag 11 S and Ag 13 S cluster cores, respectively, are protected by fac -[Rh(apt) 3 ] metalloligands, were newly synthesized from fac -[Rh(apt) 3 ] (Hapt = 3-aminopropanethiol) and Ag + in water in combination with sulfide sources. While [ 1 ] 9+ was produced by using d-penicillamine as a sulfide source, the use of HS - as a sulfide source afforded [ 2 ] 11+ without causing any precipitation of Ag 2 S. Cluster [ 1 ] 9+ was convertible to [ 2 ] 11+ via the reaction with Ag + , which led to a turn-on-type switch in photoluminescence from nonemissive [ 1 ] 9+ to emissive [ 2 ] 11+ .