Dicarboxylic Acids Induced Tandem Transformation of Silver Nanocluster

Structural transformation of metal nanoclusters (NCs) is of great ongoing interest regarding their synthesis, stability, and reactivity. Although sporadic examples of cluster transformations have been reported, neither the underlying transformation mechanism nor the intermediates are unambiguous. Herein, we have synthesized a flexible 54-nuclei silver cluster (Ag54) by combining soft (^tBuCC^–) and hard (ⁿPrCOO^–) ligands. The existence of weakly coordinated ⁿPrCOO^– enhances the reactivity of Ag54, thus facilitating the dicarboxylic acid to induce structural transformation. X-ray structural analyses reveal that Ag54 transforms to Ag₂₈ cluster-based 2D networks (Ag28a and Ag28b) induced by H₂suc (succinic acid) and H₂glu (glutaric acid), whereas with H₂pda (2,2′-(1,2-phenylene)­diacetic acid), a discrete Ag₂₈ cluster (Ag28c) is isolated. The key intermediate Ag17 that emerges during the self-dissociation of Ag54 was isolated by using cryogenic recrystallization and characterized by X-ray crystallography. The “tandem transformation” mechanism for the structure evolution from Ag54 to Ag28a is established by time-dependent electrospray ionization mass spectrometry (ESI-MS) and UV–vis spectroscopy. In addition, the catalytic activity in the 4-nitrophenol reduction follows the sequence Ag28c > Ag28b > Ag28a > Ag54 due to more bare silver sites on the surface of the Ag₂₈ cluster unit. Our findings not only open new avenues to the synthesis of silver NCs but also shed light on a better understanding of the structural transformation mechanism from one cluster to another or cluster-based metal–organic networks induced by dicarboxylates.