An Intermetallic Au24Ag20 Superatom Nanocluster Stabilized by Labile Ligands
Gang Li ( Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam)
Lars Gell ( Univ Jyvaskyla, Nanosci Ctr, Dept Chem, FI-40014 Jyvaskyla, Finland)
Hannu Häkkinen ( Univ Jyvaskyla, Nanosci Ctr, Dept Chem, FI-40014 Jyvaskyla, Finland)
- 化学化工－已发表论文 
An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)(4)(PhC C)(20)C-l2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au-12@Ag-20@Au-12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their s-bonds, leading to the formation of two types of surface staple units (PhC C-Au-L, L = PhC C- or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC C- ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility.