Photochemical Synthesis of Atomically Precise Ag Nanoclusters

Abstract

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, [Ag 25 (4-MePhC�C) 20 (Dpppe) 3 ](SbF 6 ) 3 (Ag 25 ), 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 Ag 25 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, [Ag 19 (4-t BuPhC� C) 14 (Dpppe) 3 ](SbF 6 ) 3 (Ag 19 ), [Ag 32 (4-t BuPhC�C) 22 (Dppp) 4 ](SbF 6 ) 3 (Ag 32 ), and bimetallic [Ag 22 Au 3 (4-t BuPhC�C) 20 (Dpppe) 3 ](SbF 6 ) 3 (Ag 22 Au 3 ), are produced by replacing certain ingredients. Furthermore, since the formation of Ag 19 can be regarded as a photochromatic process, a facile amine visual detection method is also presented based on this mechanism.

Photochemical Route for Synthesizing Atomically Precise Metal Nanoclusters from Disulfide

“…Photoinduced methods have been previously used for synthesizing Au nanoclusters in titanium dioxide (TiO 2 ) scaffolds and glutathione protected Au nanoclusters. , Especially, a series of atomically precise Ag nanoclusters with alkynyl and phosphine ligands on the surface have been reported very recently. In this case, an electron of certain amines is excited by light with wavelength shorter than 455 nm and transferred to Ag + , producing Ag nanoclusters …”

Recent advances in synthesis and properties of silver nanoclusters

“…Inspired by the photochemical synthesis of plasmonic nanoparticles, 52 Zhang and co-workers attempted to synthesize ligand-protected Ag NCs. 53 By irradiating a solution of suitable metal and ligand precursors along with an organic base, they successfully synthesized atomically monodisperse [Ag 25 (4-MePhCC) 20 (Dpppe) 3 ] 3+ NCs (as depicted in Fig. 3A) (where Dpppe = 1,5-bis(diphenylphosphino)pentane; 4-MePhCCH = 4-methylphenylacetylene).…”

Synthesis and characterization of Ag(I) alkynyl nanoclusters utilizing Mo VI-anchored thiacalix[4]arene metalloligands: Application in electrocatalytic CO 2 reduction

“…Atomically precise silver nanoclusters (Ag NCs) have garnered considerable attention across the chemistry and materials fields due to their visually appealing structures and catalytic applications [1][2][3][4][5][6][7][8][9]. Despite notable advancements in this area, obtaining welldefined structures of these clusters remains a formidable challenge, primarily due to the intricate arrangement of Ag ions within the aggregates and the complicating effect of noncovalent argentophilic interactions during the assembly process [10][11][12][13][14][15][16]. Protective ligands, such as thiols, alkynes, phosphines, or their combinations, play a vital role in Ag NCs assembly [17][18][19][20][21][22][23][24][25].…”