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

Abstract

The recently-increasing interest in coinage metal clusters stems from their photophysical properties, which are controlled via heterometallation. Herein, we report homometallic AgI 46 S13 clusters protected by octahedral fac-[Ir(aet)3 ] (aet=2-aminoethanethiolate) molecules and their conversion to heterometallic AgI 43 MI 3 S13 (M=Cu, Au) clusters. The reactions of fac-[Ir(aet)3 ] with Ag+ and penicillamine produced [Ag46 S13 {Ir(aet)3 }14 ]20+ ([1]20+ ), where a spherical AgI 46 S13 cluster is covered by fac-[Ir(aet)3 ] octahedra through thiolato bridges. [1]20+ was converted to [Ag43 M3 S13 {Ir(aet)3 }14 ]20+ ([1M ]20+ ) with an AgI 43 MI 3 S13 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.