Cylindrical Micelles with “Patchy” Coronas from the Crystallization-Driven Self-Assembly of ABC Triblock Terpolymers with a Crystallizable Central Polyferrocenyldimethylsilane Segment

Abstract

General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. TECHNIQUESUnless otherwise stated, all reactions were carried out on an all-glass vacuum line under nitrogen or in anMBraun glovebox under an inert purified nitrogen atmosphere.

Solution self-assembly of ABC triblock terpolymers with a central crystallizable poly(ferrocenyldimethylsilane) core-forming segment

“…51 Moreover, it has been reported that an analogous system with a PFDMS core-forming block, PS-b-PFDMS-b-PMMA, afforded cylindrical micelles that also exhibit a patchy coronal microstructure. 44 In both these cases, the coronal patchiness was attributed to immiscibility between the PS and PMMA coronaforming blocks. However, neither PS nor PMMA contain any functional groups that allow further chemical modification, such as complexation of specific patches with nanoparticles, which could lead new avenues for applications.…”

“…41,42 This enables the formation of micelles in both 1D and 2D with precise control over the micelle dimensions and results in samples with low length and area dispersities. 42,43 Furthermore, this methodology has opened convenient routes towards the formation of more complex architectures such as block co-micelles, 42 block co-platelets, 43 "patchy" micelles, [44][45][46] and hierarchical structures. [47][48][49] Living CDSA has been reported for a range of crystallizable core-forming blocks, including PFDMS, 50 polyethylene, 51 polylactide, 52 poly(εcaprolactone), 53 conjugated polymers such as poly(3-hexylthiophene), 54 poly(3-decylselenophene), 55 and oligo(p-phenylenevinylene), [56][57][58] poly(dialkylfluorene) 59 as well as molecular species that selfassemble via non-covalent interactions.…”

Recent progress in block copolymer crystallization

“…Solution assembly of triblock terpolymers also has led to interesting advances in the field of BCP crystallization. In most cases, CDSA was used to form worm‐like micellar structures with crystalline cores of either PE or PFS . While the current focus of CDSA research is related to controlled micelle growth and hierarchical assembly, triblock terpolymers provide another opportunity to tailor the corona of the micelle to form “patchy” morphologies on the micelle surface .…”

“…PS‐ b ‐PE‐ b ‐PMMA and PS‐ b ‐PFS‐ b ‐PMMA BCPs were assembled in solution to monitor the CDSA process and to create micelles with tunable, multicomponent coronas. Similar to micelles grown from mixing diblock copolymers that co‐crystallize, the central PE forms the crystalline core with two different solvophilic blocks around the exterior.…”

“…Finally, the researchers were able to selectively assemble gold nanoparticles into PMMA domains by functionalizing the methacrylate with N , N ‐dialkylethylenediamines . PFS B‐block copolymers with PS and PMMA terminal blocks also formed patchy coronas with PS or PMMA domains . Using triblocks of different PS and PMMA lengths, the rigidity of the cylindrical micelle was tailored.…”