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 AgI46S13 clusters protected by octahedral fac‐[Ir(aet)3] (aet=2‐aminoethanethiolate) molecules and their conversion to heterometallic AgI43MI3S13 (M=Cu, Au) clusters. The reactions of fac‐[Ir(aet)3] with Ag+ and penicillamine produced [Ag46S13{Ir(aet)3}14]20+ ([1]20+), where a spherical AgI46S13 cluster is covered by fac‐[Ir(aet)3] octahedra through thiolato bridges. [1]20+ was converted to [Ag43M3S13{Ir(aet)3}14]20+ ([1M]20+) with an AgI43MI3S13 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 [1Cu]20+ showed an emission band with a slightly higher energy of ca. 650 nm and a lower quantum yield, the emission band for [1Au]20+ shifted to a much higher energy of ca. 590 nm with an enhanced quantum yield. A spherical AgI46S13 cluster surrounded by 14 fac‐[Ir(2‐aminoethanethiolato)3] was newly synthesized and structurally characterized. The cluster reacted with CuI and AuI to afford Ag43Cu3S13 and Ag43Au3S13 clusters with retention of its overall structure, accompanied by a change in its photophysical properties.