The near-infrared difference spectra of 18-crown-6 in aqueous solutions have been obtained in the 1350−1650 nm region. Resolution of the difference spectra yielded the spectra of hydrated 18-crown-6 molecule and with the help of density data has allowed the determination of hydration numbers of 18-crown-6 at different concentrations (0.5−4 m). The hydration number obtained at 1 m concentration of 18-crown-6 is about ∼20, while at higher concentrations the value is around 4. These results have been interpreted in terms of hydrophobic hydration of 18-crown-6 in the dilute concentration region, resulting in clathratelike equilibria, while at higher concentrations, four water molecules remain hydrogen-bonded to the crown ether ring having D 3 d conformation. These complexed water molecules have been further differentiated into two types: (i) two water molecules doubly hydrogen-bonded (bridging) to the crown ether oxygen atoms and (ii) the other two singly hydrogen-bonded to the remaining oxygen atoms and rapidly exchangeable.
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