Understanding a ligand's effects on intra-cluster and inter-cluster assembly

Abstract

Ligands play an essential role in cluster assembly; however, understanding this behavior at the atomic level is far off. In this work, Cd₁₂Ag₃₂(S-PhOMe)₃₆(PPh)₄@Cd₆Ag₂(S-PhOMe)₆Cl₆(PPh₃)₈@Ag₆(S-PhOMe)₆Cl₂ (Abbrev. Cd₁₂Ag₃₂-1) and Cd₁₂Ag₃₂(S-c-C₆H₁₁)₃₆ (Abbrev. Cd₁₂Ag₃₂-2) were synthesized and structurally determined by single-crystal X-ray diffraction. An important finding is the selective adsorption of phosphine ligands that is caused by the different types of thiol ligands. In addition, Cd₁₂Ag₃₂-1 follows a unique stacking pattern in a superlattice with multiple inter-cluster channels. Overall, this study is helpful for an in-depth understanding of the effect of mixed ligands on nanocluster formation and the correlation between structure and properties in the nanocluster range.