Yang Mengzhou, Wu Haiming, Huang Benben, Luo Zhixun
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.
University of Chinese Academy of Sciences , Beijing 100049 , P. R. China.
J Phys Chem A. 2019 Aug 15;123(32):6921-6926. doi: 10.1021/acs.jpca.9b06502. Epub 2019 Jul 31.
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 clusters with acetylene. Well-resolved Ag clusters ( = 1-20) are produced by a self-designed magnetron sputtering source (MagS); however, on their reactions with acetylene under sufficient collisional conditions, only Ag[CH] is produced with a reasonable intensity. DFT calculations reveal that Ag clusters do not form strong Ag-C bonds with CH and Ag[CH] bears larger binding energy than the other Ag[CH] although within similar cluster-π interactions. Besides gas-phase reaction rate estimation, the relatively large noncovalent cluster-π interaction in Ag[CH] is fully demonstrated via topological analysis and natural bonding orbital analysis. Also, we illustrate both thermodynamically and kinetically favored channels in producing the Ag[CH]. This study helps in understanding metal-involved noncovalent bonds and how such weak interactions are able to tune the material function and biological activity.
我们利用定制的多离子层流管反应器与三重四极杆质谱仪联用，报告了一项关于银团簇与乙炔气相反应活性的研究。通过自行设计的磁控溅射源（MagS）产生了分辨率良好的银团簇（(n = 1 - 20)）；然而，在足够的碰撞条件下它们与乙炔反应时，仅以合理的强度生成了Ag[CH]。密度泛函理论计算表明，银团簇与CH不形成强的Ag - C键，并且尽管在类似的团簇 - π相互作用范围内，Ag[CH]的结合能比其他Ag[CH]更大。除了气相反应速率估计外，通过拓扑分析和自然键轨道分析充分证明了Ag[CH]中相对较大的非共价团簇 - π相互作用。此外，我们阐述了生成Ag[CH]的热力学和动力学有利通道。这项研究有助于理解涉及金属的非共价键以及这种弱相互作用如何能够调节材料功能和生物活性。
