Hierarchical Self-Assembly of Double-Crystalline Poly(ferrocenyldimethylsilane)-block-poly(2-iso-propyl-2-oxazoline) (PFDMS-b-PiPrOx) Block Copolymers.

The step-wise solution self-assembly of double crystalline organometallic poly(ferrocenyldimethylsilane)-block-poly(2-iso-propyl-2-oxazoline) (PFDMS-b-PiPrOx) diblock copolymers is demonstrated. Two block copolymers are obtained by copper-catalyzed azide-alkyne cycloaddition (CuAAC), featuring PFDMS/PiPrOx weight fractions of 46/54 (PFDMS30-b-PiPrOx75) and 30/70 (PFDMS30-b-PiPrOx155). Nonsolvent induced crystallization of PFDMS in acetone leads in both cases to cylindrical micelles with a PFDMS core. Afterward, the structures are transferred into water for sequential temperature-induced crystallization of the PiPrOx corona, leading to hierarchical double crystalline superstructures, which are investigated using scanning electron microscopy, wide angle X-ray scattering, and differential scanning calorimetry.