Experimental and Theoretical Study on Cation–π Interaction of the Potassium Cation with [2.2.2]Paracyclophane

• Published in: Journal of cluster science 2018, Vol.29 (1), p.21-25
• Main Authors: Makrlík, Emanuel, Sýkora, David, Böhm, Stanislav, Vaňura, Petr
• Format: Article
• Language: English
• Subjects: Benzene; Brief Communication; Catalysis; Cations; Chemistry; Chemistry and Materials Science; Hydrocarbons; Inorganic Chemistry; Ligands; Mass spectrometry; Nanochemistry; Optimization; Physical Chemistry; Potassium; Quantum chemistry; Scientific imaging; Vapor phases
• ISSN: 1040-7278; 1572-8862
• DOI: 10.1007/s10876-017-1314-x

By using electrospray ionization mass spectrometry, it was proven experimentally that the univalent potassium cation (K + ) forms with [2.2.2]paracyclophane (C 24 H 24 ) the cationic cluster [K(C 24 H 24 )] + . Further, applying quantum chemical DFT calculations, the most probable structure of the [K(C 24 H 24 )] + complex was derived. In the resulting complex with a symmetry very close to C 3 , the “central” cation K + , fully located in the cavity of the parent [2.2.2]paracyclophane ligand, is coordinated to all three benzene rings of [2.2.2]paracyclophane via cation–π interaction. Finally, the interaction energy, E (int), of the considered cation–π complex [K(C 24 H 24 )] + was found to be − 614.8 kJ mol −1 , confirming the formation of this fascinating complex species as well. It means that the [2.2.2]paracyclophane ligand can be considered as an effective receptor for the potassium cation in the gas phase. Graphical Abstract