Publication | Closed Access
Eight‐Electron Silver and Mixed Gold/Silver Nanoclusters Stabilized by Selenium Donor Ligands
136
Citations
48
References
2017
Year
The first atomically and structurally precise silver-nanoclusters stabilized by Se-donor ligands, [Ag<sub>20</sub> {Se<sub>2</sub> P(O<sup>i</sup> Pr)<sub>2</sub> }<sub>12</sub> ] (3) and [Ag<sub>21</sub> {Se<sub>2</sub> P(OEt)<sub>2</sub> }<sub>12</sub> ]<sup>+</sup> (4), were isolated by ligand replacement reaction of [Ag<sub>20</sub> {S<sub>2</sub> P(O<sup>i</sup> Pr)<sub>2</sub> }<sub>12</sub> ] (1) and [Ag<sub>21</sub> {S<sub>2</sub> P(O<sup>i</sup> Pr)<sub>2</sub> }<sub>12</sub> ]<sup>+</sup> (2), respectively. Furthermore, doping reactions of 4 with Au(PPh<sub>3</sub> )Cl resulted in the formation of [AuAg<sub>20</sub> {Se<sub>2</sub> P(OEt)<sub>2</sub> }<sub>12</sub> ]<sup>+</sup> (5). Structures of 3, 4, and 5 were determined by single-crystal X-ray diffraction. The anatomy of cluster 3 with an Ag<sub>20</sub> core having C<sub>3</sub> symmetry is very similar to that of its dithiophosphate analogue 1. Clusters 4 and 5 exhibit an Ag<sub>21</sub> and Au@Ag<sub>20</sub> core of O<sub>h</sub> symmetry composed of eight silver capping atoms in a cubic arrangement and encapsulating an Ag<sub>13</sub> and Au@Ag<sub>12</sub> 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.
| Year | Citations | |
|---|---|---|
Page 1
Page 1