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 single-thiolate-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.