Single thiolate replacement of metal nanoclusters

Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids,and thus the thiolate substitution,especially single thiolate substitution,is highly desirable for subtly tailoring the structures and properties of metal nanoclusters.However,such a single-thiolate substituting is challenging,and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the singlethiolate-substituted structure.Here,we developed a combined method,concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster,and successfully resolved their structures by single crystal X-ray crystallography,which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile.Interestingly,the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster.The bond length-related stability was also observed.Overall,this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.