Abstract
A series of five alcohols (3-methyl-2-butanol, 1-cyclopropylethanol, 1-cyclopentylethanol, 1-cyclohexylethanol, and 1-phenylethanol) was used to study the impact of the size of steric hindrance and its aromaticity on self-assembling phenomena in the liquid phase. In this Letter, we have explicitly shown that the phenyl ring exerts a much stronger effect on the self-organization of molecules via the O–H···O scheme than any other type of steric hindrance, leading to a significant decline in the size and concentration of the H-bonded clusters. Given the combination of calorimetric, dielectric, infrared, and diffraction studies, this phenomenon was ascribed to its additional proton-acceptor function for the competitive intermolecular O–H···π interactions. The consequence of this is a different packing of molecules on the short- and medium-range scale.
Highlights
A series of five alcohols (3-methyl-2-butanol, 1-cyclopropylethanol, 1-cyclopentylethanol, 1-cyclohexylethanol, and 1-phenylethanol) was used to study the impact of the size of steric hindrance and its aromaticity on self-assembling phenomena in the liquid phase
Globular-shaped isomers with a hydroxyl group highly shielded by alkyl substituents tend to agglomerate in dimers, trimers, or higher-membered rings.[6−9] In turn, terminal alcohols and their less-hindered analogues, like 6-methyl-3heptanol, form supramolecular clusters with a rather chain-like architecture of H-bonds.[10−12] This type of organization leads to the appearance of a characteristic large Debye process in the dielectric spectra, which reflects the mobility of the supramolecular structures with a nonzero resultant dipole moment.[3]
The situation becomes more complicated in phenyl alcohols, in which the bulky aromatic ring is a source of additional π···π, C−H···π, and intra- or intermolecular O−H···π interactions.[16−18] For decades, the phenyl ring was regarded as a moiety able to prevent the self-organization.[19]
Summary
A series of five alcohols (3-methyl-2-butanol, 1-cyclopropylethanol, 1-cyclopentylethanol, 1-cyclohexylethanol, and 1-phenylethanol) was used to study the impact of the size of steric hindrance and its aromaticity on self-assembling phenomena in the liquid phase. With increasing the steric hindrance size, the amplitude of the main relaxation peak declines (Figure 2b).
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