Formation of well-defined supramolecular microstructures consisting of γ-cyclodextrin and polyether —rods, cubes, plates, and nanosheets—guided by guest polymer structure

Abstract To construct well-defined microstructures, strict controls of the temperature and sophisticated techniques are generally required because microstructure formation is usually based on crystallization, which easily results in a kinetic trap of disordered structures. Herein, we report the formation of various microstructures such as rods, cubes, plates, and nanosheets via supramolecular self-assembly between γ-cyclodextrin (CD) and polyethers in water without temperature change. We revealed the relationships between the guest polymer structures and the resulting microstructure: (1) Short guest homopolymers lead to the formation of rod microstructures, whilst long congeners result in plates. (2) A hydrophilic backbone polymer is necessary to isolate the plates in water, otherwise hydrophobic interaction leads to aggregation of the plates and the formation of polycrystalline γ-CD complexes. (3) Spatial confinement of the γ-CDs on the central segment of a guest triblock copolymer plays a key role in the fabrication of nanosheets with uniform thickness.