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Rotational Spectroscopy Probes Lone Pair···π-Hole Interactions in Hexafluorobenzene-Tertiary Alkylamines Complexes

Cite this: J. Phys. Chem. Lett. 2023, 14, 23, 5335–5342
Publication Date (Web):June 5, 2023
https://doi.org/10.1021/acs.jpclett.3c00882
Copyright © 2023 American Chemical Society

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    Abstract

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    We employed microwave spectroscopy to investigate the 1:1 complexes of hexafluorobenzene with trimethylamine and quinuclidine, respectively. These complexes exhibit a C3v symmetry and are stabilized by nitrogen lone pair···π-hole interactions along the C3 axes. The N···π-center distances were determined to be 3.110(1) and 3.040(2) Å, respectively, which are shorter than that of hexafluorobenzene-ammonia at 3.2685(3) Å. Additionally, the strength of the intermolecular interaction increases with cluster size. While it was initially expected that the electron-donating effect of alkyl groups was responsible for changing the N···π interaction, the symmetry-adapted perturbation theory analysis revealed that, from hexafluorobenzene-ammonia to both hexafluorobenzene-alkylamines, electrostatic interaction actually decreases while dispersion interaction increases and becomes dominant. Interestingly, dispersion interaction decreases while electrostatic interaction increases from C6F6–N(CH3)3 to C6F6–NC7H13. The splitting pattern of the spectra indicates hexafluorobenzene rotates freely relative to its partners along the axis of the N···π-hole interactions.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.3c00882.

    • Experimental and theoretical details; The diagram of the CP-FTMW spectrometer at Fudan University; The structural informations of the complexes of C6F6–NH3, C6F6–N(CH3)3, and C6F6–NC7H13; Measured rotational transition frequencies; SAPT analysis (PDF)

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