Revisiting Dynamic Processes and Relaxation Mechanisms in a Heterocyclic Glass-Former: Direct Observation of a Transient State.

Despite decades of studies, a clear understanding of near- T g phenomena remains challenging for glass-forming systems. This review delves into the intricate molecular dynamics of the small, heterocyclic thioether, 6-methyl-2,3-dihydro-1,4-benzodithiine (MeBzS 2 ), with a particular focus on its near- T g cold crystallization and relaxation mechanisms. Investigating isothermal crystallization kinetics at various temperatures reveals a significant interplay between its molecular dynamics and recrystallization from a supercooled liquid. We also identify two independent interconversion paths between energetically privileged conformers, characterized by strained transition states. We demonstrate that these spatial transformations induce substantial alterations in the dipole moment orientation and magnitude. Our investigation also extends to the complex salt PdCl 2 (MeBzS 2 ), where we observe the transient conformers directly, revealing a direct relationship between their abundance and the local or macroscopic electric field. The initially energetically privileged isomers in an undisturbed system become less favored in the presence of an external electric field or ions, resulting even in an unexpected inversion of states. Consequently, we confirm the intramolecular character of secondary relaxation in MeBzS 2 and its mechanism related to conformational changes within the heterocyclic ring. The research is based on the combination of broadband dielectric spectroscopy, X-ray diffraction, and quantum density functional theory calculations.