Mechanistic View on the Order–Disorder Phase Transition in Amphidynamic Crystals

[Image: see text] We combine temperature-dependent low-frequency Raman measurements and first-principles calculations to obtain a mechanistic understanding of the order–disorder phase transition of 2,7-di-tert-butylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (ditBu-BTBT) and 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconducting amphidynamic crystals. We identify the lattice normal modes associated with the phase transition by following the position and width of the Raman peaks with temperature and identifying peaks that exhibit nonlinear dependence toward the phase transition temperature. Our findings are interpreted according to the “hardcore mode” model previously used to describe order–disorder phase transitions in inorganic and hybrid crystals with a Brownian sublattice. Within the framework of this model, ditBu-BTBT exhibits an ideal behavior where only one lattice mode is associated with the phase transition. TIPS-pentacene deviates strongly from the model due to strong interactions between lattice modes. We discuss the origin of the different behaviors and suggest side-chain engineering as a tool to control polymorphism in amphidynamic crystals.