Multifarious Polymorphism of a Multiblock Amphiphilic Macrocycle Bearing Thermally Responsive Polyether Segment

[Image: see text] Formation of multiple crystalline phases of a multiblock amphiphilic macrocycle AT2B is demonstrated. AT2B forms a single crystal (Cr-α) by vapor diffusion and shows reversible single-crystal-to-single-crystal transition between two crystalline phases (Cr-α and Cr-β) by a temperature change, and crystalline AT2B (Cr-β) melts at 422 K, and the cooling rate from the melt influences the phase of the solid formed. By cooling at 1.0 K min(–1), AT2B forms crystalline phases (Cr-γ and Cr-δ), which are different from both Cr-α and Cr-β. On the other hand, cooling at 2.0 K min(–1) results in the formation of an amorphous phase, and a mechanical stress also triggers a crystal-to-amorphous solid transition. Interestingly, the amorphous solid crystallizes to give the fifth crystalline phase (Cr-γ) upon heating before melting. It is suggested that these multiple phase transitions are driven by thermal conformational changes at the tetraethylene glycol chains of AT2B.