Is the kernel–staples match a key–lock match?†
Metal nanoclusters provide excellent references for understanding metal nanoparticle surfaces, which remain mysterious due to the difficulty of atomically precise characterization. Although some remarkable advances have been achieved for understanding the structure of metal nanoclusters, it is still unknown if the inner kernel–outer staples match is a key–lock match and how the surface staples influence some of the properties of metal nanoclusters. Herein, we have developed an acid-induction method for synthesizing a novel gold nanocluster whose composition is determined to be Au42(TBBT)26 (TBBT: 4-tert-butylbenzenelthiolate) by ESI-MS and single-crystal X-ray crystallography (SCXC). SCXC also reveals that Au42(TBBT)26 has an identical kernel but different staples with an existing gold nanocluster Au44(TBBT)28, indicating that the kernel–staples match is not a key–lock match and the existence of homo-ligand–homo-kernel–hetero-staples phenomenon in metal nanoclusters provides some reference for understanding the growth or transformation of metal nanoclusters. Further experiments reveal that the staples greatly contribute to the stability of gold nanoclusters and influence their photoluminescence intensity and that minute differences in the interfacial structure can lead to enhanced stability and photoluminescence.