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Updated: Oct 28, 2025

Orientational Transition in a Liquid Crystal Triggered by the Thermodynamic Growth of Interfacial Wetting Sheets
Published on: May 15, 2017
Reorientational dynamics in highly asymmetric binary low-molecular mixtures-A quantitative comparison of dielectric
Thomas Körber1, Björn Pötzschner1, Felix Krohn2
1Department of Inorganic Chemistry III and Northern Bavarian NMR Centre, University of Bayreuth, 95440 Bayreuth, Germany.
Abstract:
Previously, we scrutinized the dielectric spectra of a binary glass former made by a low-molecular high-Tg component 2-(m-tertbutylphenyl)-2'-tertbutyl-9,9'-spirobi[9H]fluorene (m-TPTS; Tg = 350 K) and low-Tg tripropyl phosphate (TPP; Tg = 134 K) [Körber et al., Phys. Chem. Chem. Phys. 23, 7200 (2021)]. Here, we analyze nuclear magnetic resonance (NMR) spectra and stimulated echo decays of deuterated m-TPTS-d4 (2H) and TPP (31P) and attempt to understand the dielectric spectra in terms of component specific dynamics. The high-Tg component (α1) shows relaxation similar to that of neat systems, yet with some broadening upon mixing. This correlates with high-frequency broadening of the dielectric spectra. The low-Tg component (α2) exhibits highly stretched relaxations and strong dynamic heterogeneities indicated by "two-phase" spectra, reflecting varying fractions of fast and slow liquid-like reorienting molecules. Missing for the high-Tg component, such two-phase spectra are identified down to wTPP = 0.04, indicating that isotropic reorientation prevails in the rigid high-Tg matrix stretching from close to Tg TPP to Tg wTPP. This correlates with low-frequency broadening of the dielectric spectra. Two Tg values are defined: Tg (wTPP) displays a plasticizer effect, whereas Tg (wTPP) passes through a maximum, signaling extreme separation of the component dynamics at low wTPP. We suggest understanding the latter counter-intuitive feature by referring to a crossover from "single glass" to "double glass" scenario revealed by recent MD simulations. Analyses reveal that a second population of TPP molecules exists, which is associated with the dynamics of the high-Tg component. However, the fractions are lower than suggested by the dielectric spectra. We discuss this discrepancy considering the role of collective dynamics probed by dielectric but not by NMR spectroscopy.
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