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).