Anion-Directed Assembly of a Bimetallic Pd/Ag Nanocluster: Synthesis, Characterization, and HER Activity.

Palladium-doped silver nanoclusters (NCs) have been highlighted for their unique physicochemical properties and potential applications in catalysis, optics, and electronics. Anion-directed synthesis offers a powerful route to control the morphology and properties of these NCs. Herein, we report a novel Pd-doped Ag NC, [Pd(H)Ag(S){SP(OPr)}] (), synthesized through the inclusion of sulfide and hydride anions.

Sulfide-mediated growth of NIR luminescent Pd/Ag atomically precise nanoclusters.

An essential feature of coinage metal nanoclusters (NCs) is their photoluminescence (PL), which spans a wide range of wavelengths from visible to near-infrared regions (NIR-I/II). A key challenge for synthetic chemists is to develop materials capable of efficient spectral change with maximum efficiency. Herein, we report novel dithiolate-protected bimetallic Pd-Ag NCs of the type [PdAgS{SP(OR)}] (R = Pr, 1Pr and Bu, 1Bu) and [PdAgS{SP(OBu)}] (2Bu).

Diselenophosphate Ligands as a Surface Engineering Tool in PdH-Doped Silver Superatomic Nanoclusters.

The first hydride-doped Pd/Ag superatoms stabilized by selenolates are reported: [PdHAg(dsep)] [dsep = SeP(OPr)] and [PdHAg(dsep)] . was derived from the targeted transformation of [PdHAg(dtp)] [dtp = SP(OPr)] by ligand exchange, whereas was obtained from the addition of trifluoroacetic acid to , resulting in a symmetric redistribution of the capping silver atoms. The transformations are all achieved while retaining an 8-electron superatomic configuration.

Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters.

The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg (dtp) ] (dtp=S P(O Pr) ) 1 and [PdHAg (dtp) ] 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg (dtp) ] 3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration.

Surface modifications of eight-electron palladium silver superatomic alloys.

Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic palladium silver nanoalloys [PdAg{SPR}], 2a-c (where R = OPr, a; OBu, b; Ph, c) via ligand exchange and/or co-reduction methods. The ligand exchange reaction on [PdAg{SP(OPr)}], 1, with [NH{SePR}] (where R = OPr, or OPr) leads to the formation of [PdAg{SeP(OPr)}] (3) and [PdAg{SeP(OPr)}] (4), respectively.