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

Abstract

We have recently reported that hydride (H - ) doped superatom (HPd@Au 8 ) + protected by eight PPh 3 ligands selectively grew into (HPd@Au 10 ) 3+ by the nucleophilic addition of two Au(I)Cl units. In the present study, (HPd@Au 8 ) + was successfully converted to unprecedented trimetallic (HPd@M 2 Au 8 ) 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@M 2 Au 8 ) 3+ (M = Au, Ag, Cu) occupy the same bridging site between the central Pd atom and the surface Au atom. (HPd@Ag 2 Au 8 ) 3+ exhibited photoluminescence at 775 nm, with the enhanced quantum yield of 0.09%, although it is structurally and electronically equivalent with (HPd@Au 10 ) 3+ . This study demonstrates that hydride-mediated growth process is a promising atomically-precise bottom-up synthetic method of new multimetallic superatoms.