Molecular Dynamics and Near-<i>T_g</i> Phenomena of Cyclic Thioethers

Abstract

This article presents the synthesis and molecular dynamics investigation of three novel cyclic thioethers: 2,3-(4′-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2-ene (compound 1), 2,3,14,15-bis(4′,4″(5″)-methylbenzo)-1,4,7,10,13,16,19,22,25-octathiacyclotetracosa-2,14-diene (compound 2), and 2,3,8,9-bis(4′,4″(5″)-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2,8-diene (compound 3). The compounds exhibit relatively high glass transition temperatures (Tg), which range between 254 and 283 K. This characteristic positions them within the so-far limited category of crown-like glass-formers. We demonstrate that cyclic thioethers may span both the realms of ordinary and sizeable molecular glass-formers, each featuring distinct physical properties. Furthermore, we show that the Tg follows a sublinear power law as a function of the molar mass within this class of compounds. We also reveal multiple dielectric relaxation processes of the novel cyclic thioethers. Above the Tg, their dielectric loss spectra are dominated by a structural relaxation, which originates from the cooperative reorientation of entire molecules and exhibits an excess wing on its high-frequency slope. This feature has been attributed to the Johari–Goldstein (JG) process. Each investigated compound exhibits also at least one intramolecular secondary non-JG relaxation stemming from conformational changes. Their activation energies range from approximately 19 kJ/mol to roughly 40 kJ/mol. Finally, we analyze the high-pressure molecular dynamics of compound 1, revealing a pressure-induced increase in its Tg with a dTg/dp coefficient equal to 197 ± 8 K/GPa.

Keywords

• glass transition
• supercooled liquid
• crown ethers
• thioethers
• dielectric spectroscopy
• relaxation process