Abstract
The molecular structure and dynamics of regioregulated poly(3-butylthiophene) (P3BT), poly(3-hexylthiophene) (P3HT), and poly(3-dodecylthiophene) (P3DDT) were investigated using Fourier-transform infrared absorption (FTIR), solid-state $^{13}\mathrm{C}$ nuclear-magnetic resonance (NMR), and differential-scanning calorimetry (DSC) measurements. In the DSC measurements, the endothermic peak was obtained around $340\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ in P3BT, and assigned to enthalpy relaxation that originated from the glass transition of the thiophene-ring twist in crystalline phase from results of FTIR, $^{13}\mathrm{C}$ cross-polarization and magic-angle spinning (CPMAS) NMR, $^{13}\mathrm{C}$ spin-lattice relaxation-time measurements, and centerband-only detection of exchange (CODEX) measurements. We defined this transition as a twist-glass transition, which is analogous to the plastic crystal--glassy crystal transition.
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