Site-Recognition-Induced Structural and Photoluminescent Evolution of the Gold–Pincer Nanocluster

The induced structural transformation provides an efficient way to precisely modulate the fine structures and the corresponding performance of gold nanoclusters, thus constituting one of the important research topics in cluster chemistry. However, the driving forces and mechanisms of these processes are still ambiguous in many cases, limiting further applications. In this work, based on the unique coordination mode of the pincer ligand-stabilized gold nanocluster Au₈(PNP)₄, we revealed the site-recognition mechanism for induced transformations of gold nanoclusters. The "open nitrogen sites" on the surface of the nanocluster interact with different inducers including organic compounds and metals and trigger the conversion of Au₈(PNP)₄ to Au₁₃ and Au₉Ag₄ nanoclusters, respectively. Control experiments verified the site-recognition mechanism, and the femtosecond and nanosecond transient absorption spectroscopy revealed the electronic and photoluminescent evolution accompanied by the structural transformation.