Cocrystallization of Two Negatively Charged Dimercaptomaleonitrile-Stabilized Silver Nanoclusters

Studies on the assembly of atomically precise metal nanoclusters
(NCs) are of great significance in the nanomaterial field, which has
attracted increasing interest in the last few decades. Herein, we
report the cocrystallization of two negatively charged atom-precise
silver nanoclusters, the octahedral [Ag62(MNT)24(TPP)6]8– (Ag62) and the truncated-tetrahedral [Ag22(MNT)12(TPP)4]4– (Ag22) in a 1:2 ratio (MNT2– = dimercaptomaleonitrile,
TPP = triphenylphosphine). As far as we know, a cocrystal containing
two negatively charged NCs has seldom been reported. Single-crystal
structure determinations reveal that the component Ag22 and Ag62 NCs both adopt core–shell
structures. In addition, the component NCs were separately obtained
by adjusting the synthetic conditions. This work enriches the structural
diversity of silver NCs and extends the family of cluster-based cocrystals.