Aromaticity effect on supramolecular aggregation. Aromatic vs. cyclic monohydroxy alcohols.

In this paper, the steric hindrance effect related to the presence of either a cyclic or aromatic ring on the self-association process in the series of monohydroxy alcohols (MAs), from cyclohexanemethanol to 4-cyclohexyl-1-butanol and from benzyl alcohol to 4-phenyl-1-butanol, was studied using X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared (FTIR) spectroscopy, Broadband Dielectric Spectroscopy (BDS) and the Pendant Drop (PD) methods. Based on FTIR results, it was shown that phenyl alcohol (PhA) and cyclohexyl alcohol (CA) derivatives reveal substantial differences in the association degree, the activation energy of dissociation, and the homogeneity of supramolecular nanoassociates suggesting that the phenyl ring exerts a stronger steric impact on the self-assembling of molecules than cyclohexyl one. Additionally, XRD data revealed that phenyl moiety introduces more heterogeneity in the organization of molecules compared to the cyclic one. The changes in the self-association process of alcohols were also reflected in differences in the molecular dynamics of the H-bonded aggregates, as well as in the Kirkwood factor, defining the long-range correlation between dipoles, which were slightly higher for CAs with respect to those determined for PhAs. Unexpectedly it was also found that the surface layers of PhAs were more organized than those formed by CAs. Thus, these findings provided insight into the impact of aromaticity on the self-assembly process, H-bonding pattern, supramolecular structure, and intermolecular dynamics of the studied alcohols.

The impact of the length of alkyl chain on the behavior of benzyl alcohol homologues - the interplay between dispersive and hydrogen bond interactions.

In this work, we examined the effect of the length of alkyl chain attached to the benzene ring on the self-assembling phenomena for a series of phenyl alcohol (PhA) derivatives, from phenylmethanol (benzyl alcohol) to 7-phenyl-1-heptanol, by means of X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Fourier Transform Infrared (FTIR) spectroscopy, and Broadband Dielectric Spectroscopy (BDS) methods. XRD data in the reciprocal and real spaces showed a gradual increase in the local order with the elongation of the alkyl chain. However, the position and full width at half maximum of the main diffraction peak exhibited a non-systematic behavior. To better understand this fact, PhAs were subjected to FTIR spectroscopic studies. These investigations revealed that the association degree and the activation energy of dissociation increase as the alkyl chain length grows. On the other hand, BDS data showed a non-monotonic variation in the Kirkwood correlation factor with increasing length of the alkyl chain, indicating a competition between interactions of the non-polar and polar parts of the molecules in the studied PhAs. Finally, it was also found that the molar surface entropy for PhAs increases with the number of methylene groups, approaching values reported for alkanes, which indicates suppression of the surface order for PhAs with a long alkyl chain. This variability of the various parameters as a function of the length of the side chain shows that the interplay between soft interactions has a strong impact on the local structure and intra and intermolecular dynamics of the studied PhAs.

Is a Dissociation Process Underlying the Molecular Origin of the Debye Process in Monohydroxy Alcohols?

Herein, we investigated the molecular dynamics as well as intramolecular interactions in two primary monohydroxy alcohols (MA), 2-ethyl-1-hexanol (2EHOH) and n-butanol (nBOH), by means of broad-band dielectric (BDS) and Fourier transform infrared (FTIR) spectroscopy. The modeling data obtained from dielectric studies within the Rubinstein approach [ Macromolecules 2013, 46, 7525-7541] originally developed to describe the dynamical properties of self-assembling macromolecules allowed us to calculate the energy barrier (Ea) of dissociation from the temperature dependences of relaxation times of Debye and structural processes. We found Ea ∼ 19.4 ± 0.8 and 5.3 ± 0.4 kJ/mol for the former and latter systems, respectively. On the other hand, FTIR data analyzed within the van't Hoff relationship yielded the energy barriers for dissociation Ea ∼ 20.3 ± 2.1 and 12.4 ± 1.6 kJ/mol for 2EHOH and nBOH, respectively. Hence, there was almost a perfect agreement between the values of Ea estimated from dielectric and FTIR studies for the 2EHOH, while some notable discrepancy was noted for the second alcohol. A quite significant difference in the activation barrier of dissociation indicates that there are probably supramolecular clusters of varying geometry or a ring-chain-like equilibrium is strongly affected in both alcohols. Nevertheless, our analysis showed that the association/dissociation processes undergoing within nanoassociates are one of the main factors underlying the molecular origin of the Debye process, supporting the transient chain model.