Shape Preserving Single Crystal to Amorphous to Single Crystal Polymorphic Transformation Is Possible

Many crystalline materials form polymorphs and undergo solid-solid transitions between different forms as a function of temperature or pressure. However, there is still a poor understanding of the mechanism of transformation. Conclusions about the transformation process are typically drawn by comparing the crystal structures before and after the conversion, but gaining detailed mechanistic knowledge is strongly impeded by the generally fast rate of these transitions. When the crystal morphology does not change, it is assumed that crystallinity is maintained throughout the process. Here we report transformation between polymorphs of ZnCl₂(1,3-diethylimidazole-2-thione)₂ which are sufficiently slow to allow unambiguous assignment of single crystal to single crystal transformation with shape preservation proceeding through an amorphous intermediate phase. This result fundamentally challenges the commonly accepted views of polymorphic phase transition mechanisms.