Abstract
Microwave complex permittivities,ɛ* =ɛ′ -Jɛ″, are reported in the 1–90 GHz frequency range for the macrocycles 18-crown-6 (18C6) and 15C5 added to acetonitrile in stoichiometric proportions, in the solvent CCl4 at 25°C. Digitized infrared spectra of the ‘CN stretch’ ν2 vibration of acetonitrile for the same systems are reported in the 2300–2200 cm−1 spectral region. The macrocycle 12C4 added to CH3CN has also been investigated in the infrared. Both the dielectric relaxation and infrared results are interpreted in terms of macrocycle-acetonitrile interactions, probably involving a methyl-hydrogen to ethereal-oxygen interaction. These interactions with CH3CN diminish in strength according to the sequence: 18C6 > 15C5 > 12C4.
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Notes and References
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In the solid state the 18C6 · 2 CH3CN complex appears to have the methyl protons of acetonitrile hydrogen-bonded to the ether oxygen atoms of 18C6 (see Ref. 6 in [41 above).
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This paper is dedicated to the memory of the late Dr C. J. Pedersen.
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Xu, M., Petrucci, S. & Eyring, E.M. Molecular dynamics and the structure of macrocycles —Solvent acetonitrile interactions. J Incl Phenom Macrocycl Chem 12, 237–251 (1992). https://doi.org/10.1007/BF01053865
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DOI: https://doi.org/10.1007/BF01053865