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

Abstract

The first hydride-doped Pd/Ag superatoms stabilized by selenolates are reported: [PdHAg 19 (dsep) 12 ] [dsep = Se 2 P(O i Pr) 2 ] 1 and [PdHAg 20 (dsep) 12 ] + 2. 1 was derived from the targeted transformation of [PdHAg 19 (dtp) 12 ] [dtp = S 2 P(O i Pr) 2 ] by ligand exchange, whereas 2 was obtained from the addition of trifluoroacetic acid to 1, resulting in a symmetric redistribution of the capping silver atoms. The transformations are all achieved while retaining an 8-electron superatomic configuration. VT-NMR attests to the good stability of the NCs in solution, and single-crystal X-ray diffraction reveals the crucial role that the interstitial hydride plays in directing the position of the capping silver atoms. The total structures are reported alongside their electronic and optical properties. 1 and 2 are phosphorescent with a lifetime of 73 and 84 μs at 77 K, respectively. The first antibacterial activity data for superatomic bimetallic Pd/Ag nanoclusters are also reported.

Hydride-doped coinage metal superatoms and their catalytic applications

“…14). 53 Correspondingly, the VT 195 Pt{ 1 H} NMR spectrum initially presents a broad singlet at −8800 ppm at 293 K, which then diverges into two separate singlets at −8753.6 and −8869.7 ppm with decreasing temperature to 173 K. This observed splitting indicates the emergence of two distinct environments for the interstitial hydride and the central Pt atom, corresponding to the two isomers of C 1 and C 3 symmetries. The result suggests that the rapid exchange of two isomeric structures occurs in solution at the ambient temperature.…”

“…A distinct difference with these superatoms is the ability to use bulk chemical separation techniques, such as routine column chromatography, to separate and purify the NC. Due to the incorporation of hydrides into the cavities of the icosahedra, this series of eight-electron superatoms all consist of a distorted icosahedron [MAg 12 ] n + (M = PdH, 52,53 PtH, 54 RhH, 55 RhH 2 55 ) stabilized by [Ag m L 12 ] n − ( m = 7–9). Until these reports, the presence of hydrides in the hydride-containing superatoms had been confirmed through methods such as NMR, and there was no direct evidence regarding the location of hydrides.…”

“…In 2022 and 2023, Liu and his collaborators used neutron diffraction to determine the position of hydrides in PtHAg 19 , RhHAg 20 , and RhH 2 Ag 19 . 51–53 In 2022, PtH was introduced into an Ag 12 icosahedron, resulting in an eight-electron [PtHAg 12 ] 5+ superatomic core. 53 Neutron diffraction confirmed the occupation of a PtAg 3 tetrahedral cavity by an interstitial hydride, Fig.…”

“…51–53 In 2022, PtH was introduced into an Ag 12 icosahedron, resulting in an eight-electron [PtHAg 12 ] 5+ superatomic core. 53 Neutron diffraction confirmed the occupation of a PtAg 3 tetrahedral cavity by an interstitial hydride, Fig. 11(a).…”

“…11(b)). 53 The dsep derivatives for both PtH and PdH have an improved symmetry in their metallic frameworks. Unlike Ag 25 , protected by thiol ligands, in systems protected by disulfide dichalcophosphate ligands, the Ag + are capping on the triangular faces of the icosahedron, leading to structural isomers.…”