Face-Centered Cubic Silver Nanoclusters Consolidated with Tetradentate Formamidinate Ligands

Growing attention has been paid to nanoclusters with face-centered cubic (fcc) metal kernels, due to its structural similarity to bulk metals. We demonstrate that the use of tetradentate formamidinate ligands facilitate the construction of two fcc silver nanoclusters: [Ag₅₂(5-F-dpf)₁₆Cl₄](SbF₆)₂ (Ag, 5-F-Hdpf = N,N'-di(5-fluoro-2-pyridinyl)formamidine) and [Ag₅₃(5-Me-dpf)₁₈](NO₃)₅ (Ag, 5-Me-Hdpf = N,N'-di(5-methyl-2-pyridinyl)formamidine). Single-crystal X-ray structural analysis revealed that the silver atoms in both clusters are in a layer-by-layer arrangement, which can be viewed as a portion of the fcc packing of silver. The nitrogen donors of amidinate ligands selectively passivate the {111} facets. All silver atoms are involved in the fcc packing, that is, no staple motifs are observed due to the linear arrangement of the four N donors of the dpf ligands. The characteristic optical absorption bands of Ag and Ag have been studied with a time-dependent density functional theory. This work provides a facile access to assembling atomically precise fcc-type nanoclusters and shows the prospect of amidinates as protecting ligands in synthesizing metal nanoclusters.