Eight‐Electron Silver and Mixed Gold/Silver Nanoclusters Stabilized by Selenium Donor Ligands

Abstract

The first atomically and structurally precise silver-nanoclusters stabilized by Se-donor ligands, [Ag {Se P(O Pr) } ] (3) and [Ag {Se P(OEt) } ] (4), were isolated by ligand replacement reaction of [Ag {S P(O Pr) } ] (1) and [Ag {S P(O Pr) } ] (2), respectively. Furthermore, doping reactions of 4 with Au(PPh )Cl resulted in the formation of [AuAg {Se P(OEt) } ] (5). Structures of 3, 4, and 5 were determined by single-crystal X-ray diffraction. The anatomy of cluster 3 with an Ag core having C symmetry is very similar to that of its dithiophosphate analogue 1. Clusters 4 and 5 exhibit an Ag and Au@Ag core of O symmetry composed of eight silver capping atoms in a cubic arrangement and encapsulating an Ag and Au@Ag centered icosahedron, respectively. Both ligand exchange and heteroatom doping result in significant changes in optical and emissive properties for chalcogen-passivated silver nanoparticles, which have been theoretically confirmed as 8-electron superatoms.

Eight‐Electron Silver and Mixed Gold/Silver Nanoclusters Stabilized by Selenium Donor Ligands

“…[4b] Thes ingle-crystal X-ray structure of 3 (Supporting Information, Figure S4), of C 3 symmetry,i sv ery similar to that of its dtp counterpart. [15] Despite the similarity between the previously reported structure of 2, [9a] and that of 4,t here are some structural differences between them in the conformation of the passivating shell (capping Ag atoms and dsep ligands). These distances are shorter than the AgÀAg distances 2.8853(11)-3.0586(9) between Ag ico and capping (m 3 -Ag) atoms.A ll Ag À Ag distances observed in 3 are similar to the distances reported for cluster 1.T he Ag ico À Se distances (avg.…”

Unified reciprocity of dithiophosphate by dichalcogenophosph(in)ate ligands on copper hydride nanoclusters via ligand exchange reaction

“…In particular, our recent attention in ligand exchange method led to the finding of intrinsically chiral inorganic diselenophosphate‐protected polyhydrido copper nanocluster [Cu 20 H 11 {Se 2 P(O i Pr) 2 } 9 ] with C 3 symmetry, which was synthesized from an achiral C 3 h symmetry based cluster [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ]. Furthermore, we were successful in the synthesis of diselenolate‐protected silver nanoclusters [Ag 20 {Se 2 P(O i Pr) 2 } 12 ], [Ag 21 {Se 2 P(OEt) 2 } 12 ] + , and Au‐Ag bimetallic nanocluster [AuAg 20 {Se 2 P(OEt) 2 } 12 ] + for the first time via ligand exchange method. Herein, we report the synthesis and structural characterization of two new polyhydrido copper nanoclusters, [Cu 20 H 11 {Se 2 P(O i Bu) 2 } 9 ] ( 2 ) and [Cu 20 H 11 {S 2 P(CH 2 CH 2 Ph) 2 } 9 ] ( 4 ), via ligand exchange protocol.…”

“…Additionally, two new copper hydrides 3 and 4 were isolated and the synthesis of cluster 4 from 3 via ligand exchange method is a remarkable instance where structural anatomy was retained at utmost precision. Our synthesis of copper hydrides via ligand exchange is parallel to the synthesis of Se‐protected silver nanoparticles . This methodology is particularly useful for the supporting ligands such as Se‐donor ligands that are not stable in solution in the presence of reducing reagents.…”

Synthesis of Two‐Electron Bimetallic Cu–Ag and Cu–Au Clusters by using [Cu13(S2CNnBu2)6(C≡CPh)4]+ as a Template

“…2018, 13,500 -504 www.chemasianj.org lated electronic structures, with some differences, however. [10] If individual oxidation states are given to the atoms constituting the [M@Cu 12 ] 11 + core, it should definitively be M(-I) and Cu(+ I). The M cent /Cu cubo natural atomic orbitals (NAO) charges are À0.54/0.69( 1'), À0.64/0.71 (2')a nd À0.81/0.73 (3').…”