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

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)(6)Cl-6(PPh3)(8)@Ag-6(S-PhOMe)(6)Cl-2 (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.