Silver Clusters Coprotected by Different Diphosphine and Thiol Ligands

The diphosphine ligands can act as auxiliary ligands for the thiol ligands to generate novel silver clusters. Here, we report five silver thiolated clusters protected by diphosphine ligands, namely, [Ag₁₁(ⁱPrS)₉(dppm)₃]­(BPh₄)₂ (1, dppm = bis­(diphenylphosphino)­methane), S@Ag₂₆(ⁱPrS)₁₆(CF₃COO)₈(dpph)₂·3DMF (2, dpph = 1,6-bis­(diphenylphosphino)­hexane), S@Ag₂₆(ⁱPrS)₁₆(CF₃COO)₈(dpppe)₂·2DMF (3, dpppe = 1,5-bis­(diphenylphosphino)­pentane), AgS₂@Ag₂₄(^tBuS)₁₈(dpppe)₂(BF₄)₃ (4), and [SO₄@Ag₂₀(ⁱPrS)₁₀(CF₃COO)₈(dpphS₂)₂]_n (5, dpphS₂ = 1,6-bis­(diphenylphosphino)­hexane disulfide). Their structures were characterized by single-crystal X-ray diffraction, which revealed that 1 presents a triangular structure covered by three diphosphine ligands, and there are strong C–H···π interactions between clusters and between clusters and counterions. Clusters 2 and 3 are olive-shaped structures, and cluster 4 is a box-type structure. Clusters 2–4 all have two diphosphine ligands at both ends. Cluster 5 is a chainlike structure connected by dpphS₂. Among them, cluster 1 exhibits photoluminescence (PL) properties, and the emission of its solution phase is red-shifted compared to the crystalline state.