Abstract:
Gold nanoclusters (AuNCs) are ideal models to study structure-property relationships due to their atomically precise compositions. Understanding this relationship is important for further explorations in photoluminescence and photocatalysis, which are highly relevant to industrial and academic work. The properties of AuNCs are mainly impacted by their ligand shells, the compositions of which are primarily modified in post-synthetic ligand exchange reactions. However, ligand exchange reactions currently have limited precision in their site selectivity. It is currently accepted that the ligand exchange reaction is primarily affected by the steric and electronic effects of the exchanging ligand, however, the impact of the ligand effects is not well understood. A recent report1 has provided insight on this topic through ligand exchange reaction on Au25(PET)18‑ [PET= phenylethanethiolate] nanoclusters. In this report, a series of porphyrinthiol derivatives are used to investigate steric and electronic effects in site-selectivity of ligand exchange reactions and the impacts they have on the structure of Au25 nanoclusters. Their methods will be discussed as well as the outlook of ligand effects in ligand exchange reactions.
(1) Suzuki, W.; Takahata, R.; Chiga, Y.; Kikkawa, S.; Yamazoe, S.; Mizuhata, Y.; Tokitoh, N.; Teranishi, T. Control over Ligand-Exchange Positions of Thiolate-Protected Gold Nanoclusters Using Steric Repulsion of Protecting Ligands. J Am Chem Soc 2022, 144 (27), 12310–12320. https://doi.org/10.1021/jacs.2c03670.
