Molecular stiffness and aromatic ring position – Crucial structural factors in the self-assembly processes of phenyl alcohols

Nowok, Andrzej; Dulski, Mateusz; Jurkiewicz, Karolina; Grelska, Joanna; Szeremeta, Anna Z.; Grzybowska, K.; Pawlus, Sebastian

doi:10.1016/j.molliq.2021.116426

Cited by 11 publications

(15 citation statements)

References 41 publications

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“…In fact, the discussions on the steric hindrance effect of molecular shape, the impact of the alkyl chain length, and the position of the OH group on the supramolecular structure in various alcohols are abundant in the literature. − However, the information on the associating phenomena of alcohols with the steric hindrance in the form of the attached phenyl group is based practically only on the dielectric and infrared spectroscopy studies and many contradictions have arisen on this topic. − First, Kalinovskaya et al and Johari et al postulated that the phenyl group in 1-phenyl-1-propanol reduces the extent of intermolecular H-bonding as the Debye-type relaxation process vanishes. Subsequently, Böhmer et al concluded that the aromatic ring only affects the supramolecular architecture of phenyl-propanols, while the structure formation through HBs is not generally suppressed by the increased steric hindrance.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Structure of Phenyl Derivatives of Butanol Isomers

et al. 2022

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Wide-angle X-ray scattering patterns were recorded for a series of aliphatic butanol isomers ( n -, iso -, sec -, tert -butanol) and their phenyl derivatives (4-phenyl-1-butanol, 2-methyl-3-phenyl-1-propanol, 4-phenyl-2-butanol, and 2-methyl-1-phenyl-2-propanol, respectively) to determine their atomic-scale structure with particular emphasis on the formation of supramolecular clusters. In addition, molecular dynamics simulations were carried out and yielded good agreement with experimental data. The combination of experimental and theoretical results allowed clarification of the origin of the pre-peak appearing at low scattering angles for the aliphatic butanols and its absence for their phenyl counterparts. It was demonstrated that the location of the hydroxyl group in the molecule of alkyl butanol, its geometry, and rigidity determine the morphology of the supramolecular clusters, while the addition of the aromatic moiety causes more disordered organization of molecules. The phenyl group significantly decreases the number of hydrogen bonds and size of the supramolecular clusters formed via the O–H···O scheme. The lower association ability of phenyl alcohols via H-bonds is additionally attenuated by the appearance of competing π–π configurations evidenced by the structural models.

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Section: Introductionmentioning

confidence: 99%

Supramolecular Structure of Phenyl Derivatives of Butanol Isomers

et al. 2022

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“…The common feature of the majority of supercooled liquids is both their nonlinear temperature dependence of the structural (α) dynamics and the nonexponential shape of the α-peak. Moreover, for some particular cases, the Debye ( D ) mode of a slower dynamics than the α-process can be additionally seen in their dielectric response due to the formation of supramolecular structure as a result of, i.e., van der Waals or Columbic interactions or hydrogen bonding. − This characteristic response is usually observed for monohydroxyl alcohols (MA, able to form excessive hydrogen bonding networks), − where it often almost completely dominated dielectric spectra (the α-mode can be detected as an excess wing in the high-frequency region). Surprisingly, a totally different scenario was observed in the case of phenyl-substituted MA (phenyl alcohols, PhAs) .…”

Section: Introductionmentioning

confidence: 99%

Nature of Dielectric Response of Phenyl Alcohols

et al. 2023

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Phenyl alcohols (PhAs) are an interesting class of materials, for which the dielectric response reveals only the presence of single prominent Debye-like (D) relaxation, interpreted as a genuine structural (α) process. Herein, we have performed dielectric and mechanical measurements on a series of PhAs characterized by the varying length of the alkyl chain and found that this interpretation is not valid. Analysis of the derivative of the real part of the complex permittivity together with the mechanical and light scattering data clearly indicated that the prominent dielectric D-like peak is actually a superposition of both cross-correlation between dipole–dipole (D-mode) and self-dipole correlation (α-process) and that the distinguished α-mode exhibits a similar (“generic”) shape of PhAs independently to their molecular weight and applied experimental technique. Therefore, the data presented herein contribute to the whole discussion focused on the dielectric response function and universality (or diversity) of the spectral shape of the α-mode of polar liquids.

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“…1–12 Model low-molecular-weight compounds that reveal the presence of pronounced D-relaxation in their dielectric response (while the structural α-mode resolves on its high-frequency flank) are monohydroxyl alcohols (MAs), forming strong H-bonding networks. 13–16 Comprehensive studies on this group of materials have shown that their chemical structure (especially, i.e. , the location of the OH-moiety or steric hindrance) has a dominant impact on both the population and the molecular architecture of the formed associates.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12] Model low-molecular-weight compounds that reveal the presence of pronounced D-relaxation in their dielectric response (while the structural a-mode resolves on its high-frequency flank) are monohydroxyl alcohols (MAs), forming strong H-bonding networks. [13][14][15][16] Comprehensive studies on this group of materials have shown that their chemical structure (especially, i.e., the location of the OH-moiety or steric hindrance) has a dominant impact on both the population and the molecular architecture of the formed associates. Along with the change within the H-bonding supramolecular structures, it was observed that both the dielectric strength of the D-process and the time separation between D and a modes strongly differ.…”

Section: Introductionmentioning

confidence: 99%