Photochemical Synthesis of Atomically Precise Ag Nanoclusters

Photochemical methods are effective for controllable synthesis of silver nanoparticles with specific sizes and shapes. Whether they are capable of fabricating Ag nanoclusters (NCs) with atomic precision is yet to be proved. In this work, we synthesize an atomically precise Ag NC, [Ag₂₅(4-MePhC≡C)₂₀(Dpppe)₃](SbF₆)₃ (Ag₂₅), via a process mediated by visible light. Its total structure is determined by X-ray crystallography. The investigation of the mechanism reveals that the formation of Ag₂₅ is triggered by a photoinduced electron-transfer (PET) process. An electron of certain amines is excited by light with wavelength shorter than 455 nm and transferred to Ag⁺. The amine is oxidized to the corresponding amine N-oxide. Such a PET process is supported by experimental and density functional theory studies. To expand the application scope of the photochemical method, another three NCs, [Ag₁₉(4-^tBuPhC≡C)₁₄(Dpppe)₃](SbF₆)₃ (Ag₁₉), [Ag₃₂(4-^tBuPhC≡C)₂₂(Dppp)₄](SbF₆)₃ (Ag₃₂), and bimetallic [Ag₂₂Au₃(4-^tBuPhC≡C)₂₀(Dpppe)₃](SbF₆)₃ (Ag₂₂Au₃), are produced by replacing certain ingredients. Furthermore, since the formation of Ag₁₉ can be regarded as a photochromatic process, a facile amine visual detection method is also presented based on this mechanism.