Is Aerogen-π Interaction Capable of Initiating the Noncovalent Chemistry of Group 18?
The interactions between atoms of noble gases and π systems are generally considered as van der Waals interaction, which have not attracted attention yet. Herein, we present high-level ab initio calculations to show the unexpected noncovalent interaction between a covalently bonded noble gas atom and a delocalized aromatic π electron using XeO3⋅benzene as the prototype. The CCSD(T)/CBS reference data show its strength amounting to -10.2 kcal mol(-1), comparable to a typical H-bond or an anion-π interaction. The energy decomposition analysis reveals that the aerogen-π interaction is favored by the electrostatic interaction (27.7%), the induction (13.4%), and the dispersion (21.6%). This interaction may prompt us to consider the noncovalent chemistry of aerogen derivatives in the near future.
Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, P. R. China.
Junjian
J
Miao
Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, P. R. China.
Bo
B
Song
Division of Interfacial Water and Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, P. R. China. gaoyi@sinap.ac.cn.
Yi
Y
Gao
D000838:Anions; D001554:Benzene / Q000737:chemistry; D004583:Electrons; D006860:Hydrogen Bonding; D011789:Quantum Theory; D055672:Static Electricity; D013816:Thermodynamics; D014978:Xenon / Q000737:chemistry*
D000838:Anions; D014978:Xenon; D001554:Benzene
ab initio calculations; aerogen-π interaction; energy decomposition analysis; supramolecular chemistry; xenon