Synergistic Effects of Pt and Cd Codoping to Icosahedral Au₁₃ Superatoms

Abstract

We synthesized a new trimetallic cluster [PtCdAu 23 (SC 2 H 4 Ph) 18 ] − , which has an icosahedral Pt@CdAu 11 superatomic core with eight electrons, and investigated how the electronic structure and optical properties of the Au@Au 12 superatomic core of [Au 25 (SC 2 H 4 Ph) 18 ] − are affected by codoping of group X and XII atoms. Spectroscopic and electrochemical measurements showed that the HOMO−LUMO (HL) gap of Pt@ CdAu 11 is larger than that of Au@Au 12 and that the photoluminescence quantum yield (PLQY) of Pt@CdAu 11 is 46 times larger than that of Au@Au 12 . To shed light on the origin of the codoping effects, a comparison was made with monodoped clusters [CdAu 24 (SC 2 H 4 Ph) 18 ] 0 and [PtAu 24 (SC 2 H 4 Ph) 18 ] 2− having the Au@ CdAu 11 and Pt@Au 12 superatomic cores, respectively. The results revealed that the increment of the HL gap of Pt@CdAu 11 is mainly because of Pt doping, while the doping of Pt and Cd synergistically enhances the PLQY of Pt@CdAu 11 .

Superatom‐in‐Superatom [RhH@Ag24(SPhMe2)18]2− Nanocluster

“…This structure contains two counterions PPh 4 + , suggesting that the synthesized NC exists in a dianionic form ((PPh 4 + ) 2 [RhHAg 24 (SPhMe 2 ) 18 ] 2− ). In addition, the results of occupancy analysis revealed that the center doping with Rh atoms produced a better fit with lower converged shift value and R 1 index (0.001 and 5.30 %, respectively) than those obtained after surface doping (−0.192 and 5.36 %, respectively), confirming that Rh occupied the central cluster position [15] . The overall framework structure of [RhHAg 24 (SPhMe 2 ) 18 ] 2− was similar to those of [MAg 24 (SPhMe 2 ) 18 ] 2− (M=Ni, Pd, and Pt) NCs [7e, 16] .…”

“…Thes ingle crystal structure presented in Figure 2a [13] In addition, the results of occupancy analysis revealed that the center doping with Rh atoms produced abetter fit with lower converged shift value and R 1 index (0.001 and 5.30 %, respectively) than those obtained after surface doping (À0.192 and 5.36 %, respectively), confirming that Rh occupied the central cluster position. [15] Theo verall framework structure of [RhHAg 24 (SPhMe 2 ) 18 ] 2À was similar to those of [MAg 24 (SPhMe 2 ) 18 ] 2À (M = Ni, Pd, and Pt) NCs. [7e, 16] Owing to the low electron density of hydrogen, the position of Hdopant could not be determined by SC-XRD.…”

Superatom‐in‐Superatom [RhH@Ag24(SPhMe2)18]2− Nanocluster

“…In addition, the results of occupancy analysis revealed that the center doping with Rh atoms produced abetter fit with lower converged shift value and R 1 index (0.001 and 5.30 %, respectively) than those obtained after surface doping (À0.192 and 5.36 %, respectively), confirming that Rh occupied the central cluster position. [15] Theo verall framework structure of [RhHAg 24 (SPhMe 2 ) 18 ] 2À was similar to those of [MAg 24 (SPhMe 2 ) 18 ] 2À (M = Ni, Pd, and Pt) NCs. [7e, 16] Owing to the low electron density of hydrogen, the position of Hdopant could not be determined by SC-XRD.…”

Dynamic hetero-metallic bondings visualized by sequential atom imaging

“…In particular, there is a lot of untapped heterometallic bonding between immiscible elements because their pure compounds are unavailable at both the bulk and atomic scale. Nevertheless, such heterometallic bonds should not be ignored, as they could provide important information regarding the design of sub-nano alloy particles (atom-hybridization) 45 – 47 or high-entropy alloys 48 .…”