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

Mengzhou Yang; Haiming Wu; Benben Huang; Zhixun Luo

doi:10.1021/acs.jpca.9b06502

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

J Phys Chem A. 2019 Aug 15;123(32):6921-6926. doi: 10.1021/acs.jpca.9b06502. Epub 2019 Jul 31.

Authors

Mengzhou Yang^{1

2}, Haiming Wu^{1

2}, Benben Huang^{1

2}, Zhixun Luo^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry , Chinese Academy of Sciences , Beijing 100190 , China.
² University of Chinese Academy of Sciences , Beijing 100049 , P. R. China.

PMID: 31314992
DOI: 10.1021/acs.jpca.9b06502

Abstract

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 Ag_n⁺ clusters with acetylene. Well-resolved Ag_n⁺ 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 Ag_n⁺ clusters do not form strong Ag-C bonds with C₂H₂ and Ag₇⁺[C₂H₂] bears larger binding energy than the other Ag_n⁺[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.