10.1021/acsomega.9b00575.s001
Haru Hirai
Haru
Hirai
Shinjiro Takano
Shinjiro
Takano
Tatsuya Tsukuda
Tatsuya
Tsukuda
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>
American Chemical Society
2019
nucleophilic addition
Theoretical calculations
PPh 3 ligands
hydride-mediated growth process
Single-crystal X-ray diffraction analysis
Pd atom
atomically-precise bottom-up
775 nm
Hydride-Mediated Regioselective Doping
Ag
multimetallic superatoms
Cu
HPd
2019-04-18 18:03:25
Journal contribution
https://acs.figshare.com/articles/journal_contribution/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_/8014559
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, 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.