Gold‐Doping of Double‐Crown Pd Nanoclusters

Abstract

Double-crown Ni, Pd, or Pt nanoclusters have attracted extensive interests due to their aesthetic structure and intriguing properties. However, their doping by other metals remains unknown until now. Herein, Pd (PET) and Pd (PET) (PET: SCH CH Ph) were successfully doped with gold and the doped nanoclusters were characterized by using multiple techniques such as mass spectrometry and X-ray crystallography. It is revealed that in the doping not one but two gold atoms replace one Pd with the other double-crown structure essentially unchanged, and the gold-doping results in the blue-shift of the maximum visible absorption, the increase of optical energy gap and the reduction of anti-aromaticity of monometal Pd nanoclusters. Importantly, it is found that Au Pd (PET) nanocluster bears chirality originating from not only the helixed Au Pd S framework, but also unanimous R or S configuration of sulfur atoms in the enantiomer. For the latter chirality origin, it was not previously reported or proposed. Au Pd (PET) reported here also represents the smallest chiral bimetal nanocluster so far to the best of our knowledge. This work advances one step toward both the tailoring of group 10 metal nanoclusters by doping and the understanding of chirality origin for metal nanoclusters.

The Synthesis of Chiral Ag4Pd2(SR)8 by Nonreplaced Galvanic Reaction

“…To our knowledge, it is the first observation of the enantiotopic phenomenon for such small Ag‐based NCs. As shown in Figure , the chirality of Ag 4 Pd 2 (SR) 8 NC is attributed to both the left‐ and right‐handed arrangement of R tails (clockwise or anticlockwise from the top) and the framework structure of Ag 4 Pd 2 S 8 , similar to the case of Au 4 Pd 2 (SR) 8 (SR:SCH 2 CH 2 Ph) nanocluster reported recently: but differentiates from those of Au 28 (SR) 20 , Au 38 (SR) 24 , Au 40 (SR) 24 , Au 102 (SR) 44 , and Au 20 (PP 3 ) 4 Cl 4 . Due to the existence of enantiomers in a 1:1 molar ratio, Ag 4 Pd 2 (SR) 8 NC can be regarded as a racemic compound, which has been successfully confirmed using chiral HPLC (high performance liquid chromatography, Figure S5, Supporting Information).…”

One-, Two-, and Three-Dimensional Self-Assembly of Atomically Precise Metal Nanoclusters

“…In 2020, we [ 142 ] conducted a detailed study on the factors responsible for the formation of 1D CSs via Au−Au bonds by using [Au 4 Pt 2 (SR) 8 ] 0 (Pt = platinum) as the NC. A similar NC, [Au 4 Pd 2 (PET) 8 ] 0 (Pd = palladium), was reported by Wu and colleagues in 2017 ( Figure 4 ) [ 143 ]. Although it was not mentioned in their paper, [Au 4 Pd 2 (PET) 8 ] 0 formed a 1D CS in its crystal ( Figure 4 ).…”

“…Use of the alloying effect. At present, there are few examples in which alloy NCs are connected to form CSs [ 142 , 143 , 146 ]. Mixing different elements leads to NCs with physical/chemical properties and functions that are different from those of monometal NCs.…”

“…S = yellow, Au = red and orange, Pd = olive, C = gray. Reproduced with permission from Reference [ 143 ]. Copyright 2017 Wiley-VCH.…”

Creation of active water-splitting photocatalysts by controlling cocatalysts using atomically precise metal nanoclusters

“…Recent studies by the other group implied that the atomically dispersed metal cocatalysts are also effective for improving the water-splitting photocatalysts. [279][280][281] In the future, it is expected that cocatalysts will be controlled in the smaller size region by using smaller ligand-protected metal clusters 114,[282][283][284][285] and thereby the effective size of cocatalysts will be elucidated in more detail.…”