Syntheses And Modification Of Silver(?) Chalcogenolate Clusters Containing Alkyl Thiolate Ligands

Silver(?) chalcogenolate clusters have been attracted great interests because of their diverse structures and various potential applications.This study presents the design and synthesis of a family of silver(?)chalcogenolate clusters containing alkyl thiol ligands.The peripheral structure of the clusters was modified by different pyridine ligands and anions.The effects of alkyl thiol ligands,solvent and anionic templates to their molecular structure were investigated.In addition,the crystal structures of the clusters were determined by single-crystal X-ray diffraction analysis.Treatment of Ag NO₃and^tBu SAg in the presence of pyridine in CH₃CN gave an one-dimensional coordination polymer[Ag₆(^tBu S)₄(Py)₂(NO₃)₂]_n(1).The use of different pyridine ligands during the assembly of[RSAg]_n(R=Et,ⁱPr,^tBu,ⁱBu)with silver trifluoroacetate(Tfa Ag)/Ag NO₃formed a range of clusters(2-11)containing dodeca-silver cores.Reactions of[RSAg]_n(R=Et,ⁱBu)with Tfa Ag in DMAc formed clusters of[Ag₁₄(Et S)₆(Tfa)₈(DMAC)₆](12)and[Ag₁₄(ⁱBu S)₆(Tfa)₈(DMAC)₄](13),while adding[(C₄H₉)₄N]₂[Mo₆O₁₉]during the reaction of[Et SAg]_nwith Tfa Ag in a mixed solvent of THF/DMF formed an ionic cluster[Ag₁₄(Et S)₆(Tfa)₁₄](H₃O⁺)₆(14).Interestingly,the three clusters 12-14 contained a same cage-like core structure of Ag₁₄S₆.In addition,the reaction of[^tBu SAg]_nwith Tfa Ag in CH₃CN/CH₃OH afforded a novel ionic cluster of[(CO₃^2-)Ag₂₀(^tBu S)₁₀(CF₃COO)₆(CH₃CN)₄](CF₃COO)₂.The CO₃^2-anions locating inside the structure acted as a template for the formation of the cluster structure while the CH₃COO^-and CH₃CN ligands surrounding the cluster stabilized the core structure.