Gas-phase Photoelectron Spectroscopy on Thiolate-protected CoinageMetal Clusters AuxAg_(44-x)(SR)30~(4-):Electron Detachment Energy from 1DSuperatomic Orbital

摘要

Gas-phase photoelectron spectroscopy (PES) is a novel tool to probe the intrinsicelectronic structures of chemically-synthesized coinage metal clusters in the absence ofexternal perturbation [1].We have applied PES to [M~(25)(SR)~(18)]-(M = Au,Ag) having anicosahedral M13 core with a closed electronic configuration of (1S)~2(1P)~6 [2,3].The presentwork is an extension of the PES studies on ligand-protected Au/Ag clusters whichaccommodate more valence electrons into higher superatomic orbitals.To this end,we chosethiolate (SR)-protected Ag cluster,[Ag44(SPhF2)30]4-(SPhF2 = 3,4-difluorobenzenethiolate) astargets.Single crystallography revealed that it hastwo-shell Ag_(12)@Ag_(20) core protected by six units ofAg2(SPhF2)5 (Fig.1 [4]).Theoretical calculationhas shown that the Ag_(12)@Ag_(20) core has a closedelectronic configuration of (1S)~2(1P)~6(1D)~(10) [4].