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Macromolecular Chemistry I:

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Werzer, O.; Resel, R.; Cherney, B.; Plank, H.; Rothmann, M.; Strohriegl, P.; Trimmel, G.; Rapallo, A.; Porzio, W.: Crystallographic structure and morphology of bithiophene-fluorene polymer nanocrystals, Polymer, 52(15), 3368-3373 (2011) -- DOI: 10.1016/j.polymer.2011.04.063
Abstract:
Nanocrystals of the polymer poly(9,9-dioctylfluorenyl-co-bithiophene) (F8T2) with a molecular weight of 3.2 kg/mol are grown in a para-xylene solution. The typical morphology of the crystals is needle like with typical widths of 50 nm and lengths of about 200 nm. The crystal structure and morphology are stable up to a temperature of 353 K. The structure solution is obtained by x-ray powder diffraction (XRD) pattern with data modelling by a stochastic global optimization procedure which allows simultaneous indexing and molecular packing determination. Final Rietveld refinement was applied on the most promising crystal structure with a = 1.376 nm, b = 3.105 nm, c = 2.690 nm and beta = 109.5 degrees within the space group C2/c choosing the polymer backbone parallel to the b-axis. The structural motifs of the molecular packing could be identified: aromatic units within a single polymer chain are slightly bent relative to the chain axis, octyl side chains are aligned along the polymer backbone and aromatic units of neighbouring molecules display a strong tendency to stack parallel to each other. XRD results of F8T2 with a molecular weight of 19 kg/mol reveal the same peak positions compared to the 3.2 kg/mol material, showing that both materials crystallise similarly and can be described by the same crystallographic unit cell. The smaller peak intensities together with the broader peak widths, however, show that the ability of crystal formation for the 19 kg/mol material is reduced.
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