A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations

Abstract

A decanuclear silver chalcogenide cluster, [Ag10(Se){Se2P(OiPr)2}8] (2) was isolated from a hydride-encapsulated silver diisopropyl diselenophosphates, [Ag7(H){Se2P(OiPr)2}6], under thermal condition. The time-dependent NMR spectroscopy showed that 2 was generated at the first three hours and the hydrido silver cluster was completely consumed after thirty-six hours. This method illustrated as cluster-to-cluster transformations can be applied to prepare selenide-centered decanuclear bimetallic clusters, [CuxAg10-x(Se){Se2P(OiPr)2}8] (x = 0–7, 3), via heating [CuxAg7−x(H){Se2P(OiPr)2}6] (x = 1–6) at 60 °C. Compositions of 3 were accurately confirmed by the ESI mass spectrometry. While the crystal 2 revealed two un-identical [Ag10(Se){Se2P(OiPr)2}8] structures in the asymmetric unit, a co-crystal of [Cu3Ag7(Se){Se2P(OiPr)2}8]0.6[Cu4Ag6(Se){Se2P(OiPr)2}8]0.4 ([3a]0.6[3b]0.4) was eventually characterized by single-crystal X-ray diffraction. Even though compositions of 2, [3a]0.6[3b]0.4 and the previous published [Ag10(Se){Se2P(OEt)2}8] (1) are quite similar (10 metals, 1 Se2−, 8 ligands), their metal core arrangements are completely different. These results show that different synthetic methods by using different starting reagents can affect the structure of the resulting products, leading to polymorphism.

Surface modifications of eight-electron palladium silver superatomic alloys

“…S7). The possibility of partial replacement of ligands cannot be excluded, however we have never encountered the partial replacement when we intend to produce dsep protected NCs from their dtp siblings via LE method [20][21][22][28][29][30][31][32][33][34] . In particular, most of the cases these reactions are associated with alteration of the metallic cores [20][21][22][28][29][30][31][32][33][34] .…”

“…The possibility of partial replacement of ligands cannot be excluded, however we have never encountered the partial replacement when we intend to produce dsep protected NCs from their dtp siblings via LE method [20][21][22][28][29][30][31][32][33][34] . In particular, most of the cases these reactions are associated with alteration of the metallic cores [20][21][22][28][29][30][31][32][33][34] . The change in metallic core is certainly a reason for the distinct color change, however we believe the change in the ligand environment plays a major role for the immediate color change.…”

“…As part of our research efforts in the synthesis of selenolate-protected Ag clusters, we have isolated a series of diselenophosphate (dsep) protected mono- and bimetallic silver clusters such as [Ag 7 (H){Se 2 P(O i Pr) 2 } 6 ] 28 , [Ag 10 (Se){Se 2 P(O i Pr) 2 } 8 ] 29 , [Ag 8 (X){Se 2 P(O i Pr) 2 } 6 ] + (X = H, Cl or Br) 30 , [Ag 11 (µ 9 -Se)(µ 3 -X) 3 {Se 2 P(O i Pr) 2 } 6 ] (X = I 31 , Br 32 ), [Ag 11 (µ 9 -I)(µ 3 -I) 3 {Se 2 P(O i Pr) 2 } 6 ] + 33 , [Ag 12 (μ 5 -X) 2 {Se 2 P(OEt) 2 } 10 ] (X = Br, I) 34 [Ag 20 {Se 2 P(O i Pr) 2 } 12 ] 20 , [Ag 21 {Se 2 P(OEt) 2 } 12 ] + 20 , [PtAg 20 {Se 2 P(OR) 2 } 12 ] (R = i Pr or n Pr) 21 and [AuAg 20 {Se 2 P(OEt) 2 } 12 ] + 20 . In fact the latter species, fabricated via a ligand exchange method, is the first structurally characterized alloy NC entirely covered by a Se ligand shell.…”

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

“…33,34 Capping two adjacent faces of an Ag 8 cube with additional silver atoms leads to the neutral cluster Se@Ag 10 {S 2 P(OR) 2 } 8 in which the central cube has been highly distorted to a trapezoidal prism. 35,36 The low symmetry of the structure leads to three different bridging patterns of the eight external dithiophosphate ligands. However, the four remaining uncapped tetragonal faces derived from the central cube before capping are each bridged a dithiophosphate ligand in the favored η 2 ,η 2 bonding mode (Fig.…”

Doping effect on a two-electron silver nanocluster

“…With the addition of an extra silver atom, the metal framework attains higher symmetry, transitioning from C 1 in Ag S6 †). 47 Moreover, in scenarios where additional copper substitution would occur, it is likely that these copper atoms would prefer being situated at the other Ag ext or Ag cap positions (Fig. S7 †).…”