The stabilities of [M12Ag32(SR)30]4- (M = Ag, Au and SR = SPhF2, SPhCF3, SPhF) clusters having the same structure but different surface ligands or counter cations were systematically studied. It was clearly revealed that a subtle structural change in the surface ligands or counter cations could significantly alter the overall stability of [M12Ag32(SR)30]4 although they all had an electronic structure of 18-electron superatom shell closure. SPhF2 was found as a better surface ligand than SPhCF3 or SPhF to stabilize [M12Ag32(SR)30]4-. And the use of more bulky [(PPhj)2N]+ as the counter cations was revealed to be more deleterious to the overall stability of [M12Ag32(SR)30]4- clusters than PPh4+. [Au12Ag32(SR)30]4- was much more stable than [Ag44(SR)30]4 with the same surface ligands and counter cations. An exceptional stability was observed on (PPh4)4[Au12Ag32(SPhF2)30] which was stable in DMF for more than 8 days in air at 80 ℃. More research efforts are still needed to deeply understand why a small structural change could result in a significant change in the stability of noble metal nanoclusters.
A remarkable solvent effect in a single-phase synthesis of monodisperse amine-capped Au nanoparticles is demonstrated.Oleylamine-capped Au nanoparticles were prepared via the reduction of HAuCU by an amine-borane complex in the presence of oleylamine in an organic solvent.When linear or planar hydrocarbon(e.g.,n-hexane,n-octane,1-octadecylene,benzene,and toluene) was used as the solvent, high-quality monodisperse Au nanoparticles with tunable sizes were obtained.However,Au nanoparticles with poor size dispersity were obtained when tetralin,chloroform or cyclohexane was used as the solvent.The revealed solvent effect allows the controlled synthesis of monodisperse Au nanoparticles with tunable size of 3-10 nm.