High-Nuclearity Silver Thiolate Clusters Constructed with Phosphonates

The n‐butylphosphonate ligand has been employed to construct three new silver(I) thiolate compounds. Single‐crystal X‐ray analysis revealed that complexes 1 and 2 are Ag48 and Ag51 coordination chain polymers, while 3 contains a discrete Ag48 cluster, in which three different kinds of silver(I) thiolate cluster shells enclose three different phosphonate‐functionalized silver(I) cluster cores, respectively. The structures of clusters in 1–3 feature three three‐shell arrangements, S@Ag12@(nBuPO3)9@Ag36S23, S@Ag11@(nBuPO3)7(MoO4)2 @Ag40S27 and MoO4@Ag12@(nBuPO3)8S6 @Ag36S24, respectively. Elaborate Ag–S nanoclusters: Two unprecedented 1D assemblies and an anionic cluster based on silver(I) thiolate cages as their surface components and phosphonate‐functionalized silver(I) clusters as cores are reported. The picture shows the outer cationic [Ag36(tBuS)24]12+ cluster that encapsulates the inner anionic [MoO4@Ag12(nBuPO3)8S6]18− cluster.