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, Cd 12 Ag 32 (S-PhOMe) 36 (PPh) 4 @Cd 6 Ag 2 (S-PhOMe) 6 Cl 6 (PPh 3 ) 8 @Ag 6 (S-PhOMe) 6 Cl 2 (Abbrev. Cd12Ag32-1) and Cd 12 Ag 32 (S- c -C 6 H 11 ) 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.