Anisotropic Extended-Chain Polymer Nanocrystals

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RANK, Christina, Manuel HÄUSSLER, Patrick RATHENOW, Michael KING, Christoph GLOBISCH, Christine PETER, Stefan MECKING, 2019. Anisotropic Extended-Chain Polymer Nanocrystals. In: Macromolecules. 52(16), pp. 6142-6148. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.9b00986

@article{Rank2019-08-27Aniso-46852, title={Anisotropic Extended-Chain Polymer Nanocrystals}, year={2019}, doi={10.1021/acs.macromol.9b00986}, number={16}, volume={52}, issn={0024-9297}, journal={Macromolecules}, pages={6142--6148}, author={Rank, Christina and Häußler, Manuel and Rathenow, Patrick and King, Michael and Globisch, Christoph and Peter, Christine and Mecking, Stefan} }

Rank, Christina Häußler, Manuel 2019-09-13T12:18:12Z Peter, Christine 2019-09-13T12:18:12Z As a concept for distinct shape polymer nanoparticles, nanoscale single crystals composed of a crystallizable chain with lyophilic end groups are explored. This differs from much studied block copolymer nanoparticles and nanostructures, in which the second (noncrystalline) blocks’ spacial demand impacts the overall structure and blurs the cores’ anisotropic shape. For precise C<sub>48</sub> polyethylene telechelics X(CH<sub>2</sub>)<sub>46</sub>X (X = COO<sup>–</sup>M<sup>+</sup> or CH<sub>2</sub>SO<sub>3</sub><sup>–</sup>M<sup>+</sup>, with M<sup>+</sup> = Na<sup>+</sup>, K<sup>+</sup>, or Cs<sup>+</sup>) as a relevant model system, a combined experimental and atomistic-level simulation study reveals them to form extended-chain, single-crystalline nanoparticles sandwiched by a layer of head groups. Their microscopic structure, order, and the resulting overall shape are decisively impacted by the mutual repulsion of the head groups, itself determined by the degree of ion pairing with the counterions and the size of the head groups. This leads to the bending of the chains at the lateral side of the crystal, preventing the particles from agglomeration, and to a chain tilt of the monolayer, thus reducing its thickness. By comparison, for a shorter analogue Cs<sup>+</sup> <sup>–</sup>OOC(CH<sub>2</sub>)<sub>21</sub>COO<sup>–</sup> Cs<sup>+</sup>, the attractive van der Waals interactions between the hydrocarbon chains are not sufficient to overcome the head group repulsion, resulting in nanoparticle break up. These insights are instrumental for understanding and designing anisotropic organic polymer particles exploiting the principles of polymer crystallinity, which are also predestined for particle assembly. Mecking, Stefan eng Globisch, Christoph Rathenow, Patrick Rathenow, Patrick King, Michael Peter, Christine Mecking, Stefan 2019-08-27 Anisotropic Extended-Chain Polymer Nanocrystals Rank, Christina King, Michael Häußler, Manuel Globisch, Christoph

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