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

New homochiral (AgRhIII)-Rh-I nanoclusters,Delta(6)/?(6)-[Ag11S{Rh(apt)(3)}(6)](9+) and Delta(6)/?(6)-[Ag13S{Rh(apt)(3)}(6)](11+) (Hapt = 3-aminopropanethiol), which are produced from fac-[Rh(apt)(3)] and Ag+ dependent on the sulfidesource (penicillamine vs NaSH), are reported. Thetwo homochiral (AgRhIII)-Rh-I nanoclusters,Delta(6)/?(6)-[Ag11S{Rh(apt)(3)}(6)](9+) ([1](9+)) and Delta(6)/?(6)-[Ag13S{Rh(apt)(3)}(6)](11+) ([2](11+)), in which Ag11S and Ag13S 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 asa sulfide source, the use of HS- as a sulfide sourceafforded [2](11+) without causing any precipitationof Ag2S. Cluster [1](9+) was convertibleto [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+).

Automated summary

New homochiral (AgRhIII)-Rh-I nanoclusters, Delta(6)/?(6)-[Ag11S{Rh(apt)(3)}(6)](9+) and Delta(6)/?(6)-[Ag13S{Rh(apt)(3)}(6)](11+) were successfully synthesized using different sulfide sources in water. The cluster cores of [1](9+) and [2](11+), protected by fac-[Rh(apt)(3)] metalloligands, consist of Ag11S and Ag13S, respectively. Photoluminescence switch from nonemissive [1](9+) to emissive [2](11+) was achieved by converting [1](9+) to [2](11+) through the reaction with Ag+.