A 60‐nuclear silver sulfide nanocluster with a highly positive charge (1) has been synthesized by mixing an octahedral RhIII complex with 2‐aminoethanethiolate ligands, silver(I) nitrate, and d‐penicillamine in water under mild conditions. The spherical surface of 1 is protected by the chiral octahedral RhIII complex, with cleavage of the C−S bond of the d‐penicillamine supplying the sulfide ions. Although 1 does not contain d‐penicillamine, it is optically active because of the enantiomeric excess of the RhIII molecules induced by chiral transfer from d‐penicillamine. 1 can accommodate/release external Ag+ ions and replace inner Ag+ ions by Cu+ ions. The study demonstrates that a thiolato metal complex and sulfur‐containing amino acid can be used as cluster‐surface‐protecting and sulfide‐supplying regents, respectively, for creating chiral, water‐soluble, structurally precise silver sulfide nanoclusters, the properties of which are tunable through the addition/removal/exchange of Ag+ ions.

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.

The two homochiral Ag I Rh III nanoclusters, Δ 6 /Λ 6 -[Ag 11 S{Rh(apt) ), 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+ .

A60-nuclear silver sulfide nanocluster with ahighly positive charge (1)h as been synthesized by mixing an octahedral Rh III complex with 2-aminoethanethiolate ligands, silver(I) nitrate,a nd d-penicillamine in water under mild conditions.The spherical surface of 1 is protected by the chiral octahedral Rh III complex, with cleavage of the C À Sbond of the d-penicillamine supplying the sulfide ions.Although 1 does not contain d-penicillamine,i ti so ptically active because of the enantiomeric excess of the Rh III molecules induced by chiral transfer from d-penicillamine. 1 can accommodate/release external Ag + ions and replace inner Ag + ions by Cu + ions.The study demonstrates that at hiolato metal complex and sulfurcontaining amino acid can be used as cluster-surface-protecting and sulfide-supplying regents,r espectively,f or creating chiral, water-soluble,s tructurally precise silver sulfide nanoclusters, the properties of which are tunable through the addition/ removal/exchange of Ag + ions.

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