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>
journal contribution
posted on 2019-04-18, 18:03 authored by Haru Hirai, Shinjiro Takano, Tatsuya TsukudaWe 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, 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@M<sub>2</sub>Au<sub>8</sub>)<sup>3+</sup> (M = Au, Ag, Cu) occupy the same bridging
site between the central Pd atom and the surface Au atom. (HPd@Ag<sub>2</sub>Au<sub>8</sub>)<sup>3+</sup> exhibited photoluminescence at
775 nm, with the enhanced quantum yield of 0.09%, although it is structurally
and electronically equivalent with (HPd@Au<sub>10</sub>)<sup>3+</sup>. This study demonstrates that hydride-mediated growth process is
a promising atomically-precise bottom-up synthetic method of new multimetallic
superatoms.
