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Synthesis of Trimetallic (HPd@M2Au8)3+ Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au8)2.

ABSTRACT: We have recently reported that hydride (H-) doped superatom (HPd@Au8)+ protected by eight PPh3 ligands selectively grew into (HPd@Au10)3+ by the nucleophilic addition of two Au(I)Cl units. In the present study, (HPd@Au8)+ was successfully converted to unprecedented trimetallic (HPd@M2Au8)3+ superatoms (M = Ag, Cu) by controlled doping of two Ag(I)Cl or Cu(I)Cl units, respectively. Single-crystal X-ray diffraction analysis demonstrated that two Ag(I) or Cu(I) ions were regioselectively incorporated. Theoretical calculations suggested that hydrogens in (HPd@M2Au8)3+ (M = Au, Ag, Cu) occupy the same bridging site between the central Pd atom and the surface Au atom. (HPd@Ag2Au8)3+ exhibited photoluminescence at 775 nm, with the enhanced quantum yield of 0.09%, although it is structurally and electronically equivalent with (HPd@Au10)3+. This study demonstrates that hydride-mediated growth process is a promising atomically-precise bottom-up synthetic method of new multimetallic superatoms.

SUBMITTER: Hirai H 

PROVIDER: S-EPMC6648303 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Synthesis of Trimetallic (HPd@M<sub>2</sub>Au<sub>8</sub>)<sup>3+</sup> Superatoms (M = Ag, Cu) via Hydride-Mediated Regioselective Doping to (Pd@Au<sub>8</sub>)<sup>2</sup>.

Hirai Haru H   Takano Shinjiro S   Tsukuda Tatsuya T  

ACS omega 20190418 4

We have recently reported that hydride (H<sup>-</sup>) doped superatom (HPd@Au<sub>8</sub>)<sup>+</sup> protected by eight PPh<sub>3</sub> ligands selectively grew into (HPd@Au<sub>10</sub>)<sup>3+</sup> by the nucleophilic addition of two Au(I)Cl units. In the present study, (HPd@Au<sub>8</sub>)<sup>+</sup> was successfully converted to unprecedented trimetallic (HPd@M<sub>2</sub>Au<sub>8</sub>)<sup>3+</sup> superatoms (M = Ag, Cu) by controlled doping of two Ag(I)Cl or Cu(I)Cl units, respectiv  ...[more]

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