Influence of Molecular Architecture on the Dynamics of H-Bonded Supramolecular Structures in Phenyl-Propanols.

Relaxation behavior of monohydroxy alcohols (monoalcohols) in broadband dielectric spectroscopy (BDS) is usually dominated by the Debye process. This process is regarded as a signature of the dynamics of transient supramolecular structures formed by H-bonding. In phenyl-propanols, the steric hindrance of the phenyl ring is assumed to influence chain formation and thereby to decrease or even suppress the intensity of the Debye process. In the present paper, we study this effect in a systematic series of structural isomers of phenyl-1-propanol in comparison with 1-propanol. It turns out that by combining BDS, photon correlation spectroscopy (PCS), and calorimetry, the dynamics of supramolecular structures can be uncovered. While light scattering spectra show the same spectral shape of the main relaxation for all investigated monoalcohols, the dielectric spectra differ in the Debye contribution. Thus, it becomes possible for the first time to unambiguously disentangle both relaxation modes in the dielectric spectra. It turns out that the Debye relaxation becomes weaker, the closer the position of the phenyl ring is to the hydroxy group, in accordance with the analysis of the Kirkwood/Fröhlich correlation factor. Even in 1-phenyl-1-propanol, which has the phenyl group attached at the closest position to the hydroxy group, we can separate a Debye contribution in the dielectric spectrum. From this, we conclude that structure formation through hydrogen bonds is not generally suppressed by the increased steric hindrance of the phenyl ring, but rather an equilibrium of ring and chain-like structures is shifted toward ring-like shapes on shifting the phenyl ring closer to the hydroxy group. Moreover, the shape of the α-relaxation, as monitored by PCS, is the same as the self-part of the correlation in BDS, remains unaffected by the degree of hydrogen bonding and is the same among the investigated alcohols.