Ligand Modification of Au₂₅ Nanoclusters for Near-Infrared Photocatalytic Oxidative Functionalization

Abstract

The inorganic–organic interface between metal catalysts and their substrates greatly influences reaction processes, but few studies of this interface have been conducted for a detailed understanding of its structure. Herein, we describe the synthesis and structural determination of an arylthiolated Au25(F-Ph)18 – nanocluster and characterize in detail the key roles of its ligands in photocatalyzed oxidative functionalization reactions. The most significant findings are that (i) interactions are established between ligands to avoid distortion of the geometric structure, limit the Jahn–Teller effect, and protect the nanocluster from oxidization and (ii) the low energy gap (HOMO–LUMO) of the synthetic clusters enables three types of photocatalytic oxidative functionalization reactions by near-infrared light (850 nm).

Doping‐Mediated Energy‐Level Engineering of M@Au12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis

“…The former has the O1 potential (−0.167 V vs Fc + /Fc 0 ) [24] and excited lifetime (5.7 μs) [24] comparable to those of IrAu 12 . The latter is the representative Au 13 superatom and is known to act as a photosensitizer for the generation of 1 O 2 [46, 47] . As shown in Table 1, RuAu 12 ‐m exhibited comparable activity to RhAu 12 , but lower activity than IrAu 12 and PtAu 12 .…”

Doping‐Mediated Energy‐Level Engineering of M@Au12 Superatoms (M=Pd, Pt, Rh, Ir) for Efficient Photoluminescence and Photocatalysis

“…The latter is the representative Au 13 superatom and is known to act as a photosensitizer for the generation of 1 O 2 . [46,47] As shown in Table 1, RuAu 12 -m exhibited comparable activity to RhAu 12 , but lower activity than IrAu 12 and PtAu 12 . [Au 25 (PET) 18 ] À showed no catalytic ability probably due to the short (ns-order) photoexcited lifetime.…”

Gold nanoclusters: Photophysical properties and photocatalytic applications

“…1 O 2 produced by photoexciting Au 25 clusters can catalyze the oxidation of organic sulfide to sulfoxide with selectivity close to 100%. Besides, Zhu et al also find that the arylthiolated Au 25 (F-Ph) 18 − nanocluster with NIR emission can photosensitize 3 O 2 to produce 1 O 2 for photocatalytic oxidative functionalization of sulfide, β-ketoesters, and 2-aryl-1,2,3,4-tetrahydroisoquinoline ( Wang et al, 2022 ).…”