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 @Ag36 S23 , S@Ag11 @(nBuPO3 )7 (MoO4 )2 @Ag40 S27 and MoO4 @Ag12 @(nBuPO3 )8 S6 @Ag36 S24 , respectively.