Abstracts from the NIHR INVOLVE Conference 2017

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Synthesis and Bulk Self-Assembly of ABC Star Terpolymers with a Polyferrocenylsilane Metalloblock

The synthesis, characterization, and self-assembly of a range of ABC star polymers with arms of polyisoprene, poly­(ferrocenylethylmethylsilane), and polystyrene is reported. A library of azide-functionalized polyisoprene and poly­(ferrocenylethylmethylsilane) homopolymers were prepared by living anionic polymerization. Polystyrene was synthesized by living anionic polymerization and quenched with 3-triisopropylsilylethynyl-5-trimethylsilylethynylbenzaldehyde, yielding “core-functionalized” polystyrene with two different alkyne units. The azide-functionalized monomers were sequentially attached to core-functionalized polystyrene via copper­(I)-catalyzed azide–alkyne cycloaddition reactions, giving polystyrene–polyisoprene–poly­(ferrocenylethylmethylsilane) ABC star terpolymers with different compositions and narrow dispersities. Additionally, a chlorosilane route was employed as an alternative means of synthesis. Bulk films of each star terpolymer were prepared, and their self-assembly was analyzed by transmission electron microscopy. The formation of a diverse range of morphologies was observed, including lamellae with alternating cylinders and two different Archimedean tiling patterns

Ordered Nanoscale Archimedean Tilings of a Templated 3‑Miktoarm Star Terpolymer

The directed self-assembly of 3-miktoarm star terpolymer chains (polyisoprene-<i>arm</i>-polystyrene-<i>arm</i>-polyferrocenylethylmethylsilane (3 μ-ISF)) into 2D Archimedean tilings is described. A morphological change from (4.8²) to (6³) tiling is reported in the 3 μ-ISF thin film blended with PS homopolymer when a greater swelling of PI is achieved during the solvent annealing process. Highly oriented (4.8²) tilings were produced by templating the self-assembled three colored structures in blended thin films. The use of (4.8²) and (6³) tilings as nanolithographic masks to transfer square and triangular hole arrays into the substrate is also demonstrated