Cluster-π Interactions Cause Size-Selective Reactivity of Cationic Silver Clusters with Acetylene: The Distinctive Ag7+[C2H2].

Utilizing a customized multiple-ion laminar flow tube reactor in tandem with a triple quadrupole mass spectrometer, we report a study of the gas-phase reactivity of Agn+ clusters with acetylene. Well-resolved Agn+ clusters (n = 1-20) are produced by a self-designed magnetron sputtering source (MagS); however, on their reactions with acetylene under sufficient collisional conditions, only Ag7+[C2H2] is produced with a reasonable intensity. DFT calculations reveal that Agn+ clusters do not form strong Ag-C bonds with C2H2 and Ag7+[C2H2] bears larger binding energy than the other Agn+[C2H2] although within similar cluster-π interactions. Besides gas-phase reaction rate estimation, the relatively large noncovalent cluster-π interaction in Ag7+[C2H2] is fully demonstrated via topological analysis and natural bonding orbital analysis. Also, we illustrate both thermodynamically and kinetically favored channels in producing the Ag7+[C2H2]. This study helps in understanding metal-involved noncovalent bonds and how such weak interactions are able to tune the material function and biological activity.