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.