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Crystal Structures of Two New Gold–Copper Bimetallic Nanoclusters: Cu<sub><i>x</i></sub>Au<sub>25–<i>x</i></sub>(PPh<sub>3</sub>)<sub>10</sub>(PhC<sub>2</sub>H<sub>4</sub>S)<sub>5</sub>Cl<sub>2</sub><sup>2+</sup> and Cu<sub>3</sub>Au<sub>34</sub>(PPh<sub>3</sub>)<sub>13</sub>(<sup>t</sup>BuPhCH<sub>2</sub>S)<sub>6</sub>S<sub>2</sub><sup>3+</sup>
53
Citations
24
References
2017
Year
Herein, we report the synthesis and atomic structures of the cluster-assembled Cu<sub>x</sub>Au<sub>25-x</sub>(PPh<sub>3</sub>)<sub>10</sub>(PhCH<sub>2</sub>CH<sub>2</sub>S)<sub>5</sub>Cl<sub>2</sub><sup>2+</sup> and Cu<sub>3</sub>Au<sub>34</sub>(PPh<sub>3</sub>)<sub>13</sub>(<sup>t</sup>BuPhCH<sub>2</sub>S)<sub>6</sub>S<sub>2</sub><sup>3+</sup> nanoclusters (NCs). The atomic structures of both NCs were precisely determined by single-crystal X-ray crystallography. The Cu<sub>x</sub>Au<sub>25-x</sub>(PPh<sub>3</sub>)<sub>10</sub>(PhC<sub>2</sub>H<sub>4</sub>S)<sub>5</sub>Cl<sub>2</sub><sup>2+</sup> NC was assembled by two icosahedral M<sub>13</sub> via a vertex-sharing mode. The Cu atom partially occupies the top and waist sites and is monocoordinated with chlorine or thiol ligands. Meanwhile, the Cu<sub>3</sub>Au<sub>34</sub>(PPh<sub>3</sub>)<sub>13</sub>(<sup>t</sup>BuPhCH<sub>2</sub>S)<sub>6</sub>S<sub>2</sub><sup>3+</sup> NC can be described as three 13-atom icosahedra sharing three vertexes in a cyclic fashion. The three Cu atoms all occupy the internal positions of the cluster core. What is more important is that all three Cu atoms in Cu<sub>3</sub>Au<sub>34</sub> are monocoordinated by the bare S atoms. The absorption spectra of the as-synthesized bimetallic NCs reveal that the additional metal doping and different cluster assemblies affect the electronic structure of the monometallic NCs.
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