Heterometallation of Photoluminescent Silver(I) Sulfide Nanoclusters Protected by Octahedral Iridium(III) Thiolates

The recently‐increasing interest in coinage metal clusters stems from their photophysical properties, which are controlled via heterometallation. Herein, we report homometallic Ag I 46 S 13 clusters protected by octahedral fac ‐[Ir(aet) 3 ] (aet=2‐aminoethanethiolate) molecules and their conversion to heterometallic Ag I 43 M I 3 S 13 (M=Cu, Au) clusters. The reactions of fac ‐[Ir(aet) 3 ] with Ag + and penicillamine produced [Ag 46 S 13 {Ir(aet) 3 } 14 ] 20+ ([ 1 ] 20+ ), where a spherical Ag I 46 S 13 cluster is covered by fac ‐[Ir(aet) 3 ] octahedra through thiolato bridges. [ 1 ] 20+ was converted to [Ag 43 M 3 S 13 {Ir(aet) 3 } 14 ] 20+ ([ 1 M ] 20+ ) with an Ag I 43 M I 3 S 13 cluster by treatment with M + , retaining its overall structure. [ 1 ] 20+ was photoluminescent and had an emission band ca. 690 nm that originated from an S‐to‐Ag charge transfer. While [ 1 Cu ] 20+ showed an emission band with a slightly higher energy of ca. 650 nm and a lower quantum yield, the emission band for [ 1 Au ] 20+ shifted to a much higher energy of ca. 590 nm with an enhanced quantum yield.