Synthese und Eigenschaften von supramolekularen zylindrischen Strukturen aus Blockcopolymeren mit organometallischen Baueinheiten
Final Report Abstract
We succeeded to prepare block copolymers with a new metal containing poly(ferrocenylsilane) block. The synthesis of poly(ferrocenyldiethylsilane) PEDES block copolymers and the self-assembly studies of the obtained block copolymers represent the first examples of diblock copolymers forming cylindrical structures in solution with a metallo block other than poly(ferrocenyldimethylsilane) PFDMS. In addition, diblock copolymers containing the germane analogue of PFDMS, i.e. poly(ferrocenyldimethyl germane) PFDMG, were prepared and their self-assembly properties were studied (collaboration wilh Nga Sze leong in Bristol). Furthermore, we were able to prepare monodisperse cylindrical micelles with controlled length. Therefore, a new sonication protocol for the disruption of cylindrical micelles was developed which yielded very short monodisperse stub-like micelles which were useful as seed material (i.e. initiator) for the epitaxial growth of cylindrical micelles. Using a similar approach we prepared monodisperse amphiphilic block co-micelles containing segments of different corona solubility. First self-assembly studies of these amphiphilic block micelles indicate that these species are prone to self-assembly into "super-micelles", similar to the selfassembly of amphiphilic copolymers in selective solvents. We also succeeded to prepare unprecedented nanostructures based on the self-assembly of diblock copolymers with crystalline metallo-blocks. Scarf-like architectures were obtained by treating platelet like seed structures with cylinder forming diblock copolymers containing semicrystalline PFDMS core blocks. Furthermore, a brush of cylindrical micelles on a solid substrate was fabricated by using a crystalline thin film of PFDMS as substrate for the epitaxial growth of cylindrical micelles. We also synthesized cylindrical block co-micelles containing diblock copolymers with different core forming blocks, i.e. PFDMS and PFDMG, which is the first example of heteroepitaxial micelle growth.
Publications
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"Complex and hierarchical micelle architectures from diblock copolymers using living, crystallization-driven polymerizations". Nature Materials 2009, 8, 144-150
Torben Gädt, Nga Sze leong, Graeme Cambridge, Mitchell A. Winnik, Ian Manners
