Hydride Doping Effects on the Structure and Properties of Eight-Electron Rh/Ag Superatoms: The [RhH_x@Ag_21–x{S₂P(OⁿPr)₂}₁₂] (x = 0–2) Series

Abstract

Three hitherto unknown eight-electron rhodium/silver alloy nanoclusters, [RhAg21{S2P(O n Pr)2}12] (1), [RhHAg20{S2P(O n Pr)2}12] (2), and [RhH2Ag19{S2P(O n Pr)2}12] (3), have been isolated and fully characterized. Cluster 1 contains a regular Rh@Ag12 icosahedral core, whereas 2 and 3 exhibit distorted RhH@Ag12 and RhH2@Ag12 icosahedral cores. The single-crystal neutron structure of 2 located the encapsulated hydride at the center of an enlarged RhAg3 tetrahedron. A similar position was found by neutron diffraction for one of the hydrides in 3, whereas the other hydride is trigonally coordinated to Rh and an elongated Ag–Ag edge. The solid-state structures of 1–3 possess C 1 symmetry due to the asymmetric arrangement of the surrounding capping Ag atoms. Our investigation shows that the insertion of one hydride dopant provokes the elimination of one capping silver atom on the cluster surface, resulting in the general formula [RhH x @Ag21–x {S2P(O n Pr)2}12] (x = 0–2), which maintains the same number of cluster electrons as well as neutral charge. Clusters 1–3 exhibit an intense emission band in the NIR region. Contrarily to their PdAg21 and PdHAg20 relatives, the 4d orbitals of the encapsulated heterometal are somewhat involved in the optical processes.

Systematics of stable copper and silver clusters protected by small bite chelating bidentate sulfur and selenium ligands related to their polyhedral cavities: analogies to aliphatic compounds and three-dimensional spherical aromatic systems

“…46 A series of eight-electron subvalent clusters of the general formula RhH x @Ag 21− x {S 2 P(O n Pr) 2 } 12 ( x = 0 to 2) with interstitial rhodium atoms is known in which the interstitial rhodium is formally a monoanion Rh − in order to have a closed-shell d 10 configuration. 47 The number of silver caps on the Ag 12 icosahedron in these mixed Ag–Rh clusters is dependent on the number of interstitial hydride ligands.…”

Hydride-doped coinage metal superatoms and their catalytic applications

“…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.…”

“…Moreover, by employing 1 H decoupling with the 195 Pt nucleus across different chemical shift ranges at low temperatures, it becomes possible to ascertain the specific Pt atom to which the hydride is bonded. The VT NMR experiments are similarly practical in observing isomerization phenomena within other hydride-containing, Pd-doped Ag alloys, 54,55 offering a broader application for understanding further illuminates such nanoclusters’ intricate dynamics and structural variations.…”

Structural modification and performance regulation of atomically precise metal nanoclusters by phosphine

“…To achieve the purpose of multidirectional regulation of the structure of metal nanoclusters, Kang et al ( 2017) attempted to incorporate triphenylphosphine and 1adamantanethiol (HSAdm) into PtAg 24 (SPhMe 2 ) 18 nanoclusters. Interestingly, although the phosphine-LEIST reaction occurred on the cluster surface, the template nanocluster did not undergo a topdown transformation; on the contrary, larger PtAg 28 (SAdm) 18 (PPh 3 ) 4 was generated [85]. The metal framework of Pt 1 Ag 28 nanocluster has discrete Ag 4 S 6 P 1 motifs, an overall surface shell (Ag 16 S 18 P 4 ), and a tetrahedral structure.…”