Cd Atom Goes into the Interior of Cluster Induced by Directional Consecutive Assembly of Tetrahedral Units on an Icosahedron Kernel

Abstract

“Core sliding” in metal nanoclusters drives the reconstruction of external structural units and provides an ideal platform for mapping their precise transformation mechanism and evolution pathway. However, observing the movement behavior of metal atoms in experiments is still challenging because of the uncertain stability of intermediates. In this work, a series of Au–Cd alloy nanoclusters with continuously assembled kernels (one icosahedral building block assembled with 0 to 3 tetrahedral units) were constructed. As the assembly continued, it eventually led to the Cd atom doping into the inner positions of the clusters. Importantly, the Cd doped into the interior of the cluster exhibits a different behavior than the surface or external Cd atoms (dispersion doping vs localized occupy), which provides experimental evidence of the sliding behavior in the nanocluster kernel. Furthermore, density functional theory (DFT) calculations reveal that this sliding behavior in the inner sites of nanoclusters is an energetically favorable process. In addition, these Au–Cd nanoclusters exhibit tunable optical properties with different assembly patterns in their kernels.

[Au14(2-SAdm)9(Dppe)2]+: a gold nanocluster with a crystallization-induced emission enhancement phenomenon

“…The Au 7 kernel can be regarded as the combination of two Au 4 tetrahedrons via vertexsharing mode. The binding mode of Au 3 (SR) 3 (Dppe) 1 and Au 1 (SR) 1 (Dppe) 1 motifs is comparable with that of Au 3 (SR) 4 and Au 1 (SR) 2 , respectively, in which one of the terminal thiolate ligands was replaced by a diphosphine. This type of motif was also found previously in other Au NCs protected by thiolate and diphosphine ligands.…”

“…In recent years, metal nanoclusters exhibiting ultra-small size (o3 nm), precise structures and excellent physicochemical properties have received more and more attention. [1][2][3][4][5] Among them, photoluminescence (PL) in nanoclusters is one of the most attractive and fascinating properties. [6][7][8] Compared with organic fluorophores or semiconductor quantum dots (QDs), PL nanoclusters generally exhibit superior photostability and biocompatibility.…”

Tailoring Carbon Tails of Ligands on Au52(SR)32 Nanoclusters Enhances the Near-Infrared Photoluminescence Quantum Yield from 3.8 to 18.3%

“…form the shell . By adopting different synthetic methods, the core (or kernel) of Au NCs can be tailored and a rich library of structures such as the tetrahedron, cuboctahedron, and icosahedron has been constructed. − Such diversity provides rich opportunities for tailoring the PL properties. , …”

Associating Co single atoms with RuO2nanoparticles anchor on nitrogen-doped ultrathin porous carbon nanosheets as effective bifunctional oxygen electrocatalysts for rechargeable Zn–air batteries

“…Chen et al designed a strategy to stabilize Cu atoms with silica, which improved the stability of the catalyst by forming abundant Cu–O–Si interfaces. 31…”