Journal
MACROMOLECULAR CHEMISTRY AND PHYSICS
Volume 216, Issue 6, Pages 685-695Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/macp.201400541
Keywords
block copolymers; conjugated polymers; crystallization; living polymerization; self-assembly
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Funding
- European Research Council (ERC)
- Bristol Centre for Functional Nanomaterials
- Natural Sciences and Engineering Research Council (NSERC) of Canada
- EPSRC [EP/K03927X/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K03927X/1] Funding Source: researchfish
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The crystallization-driven self-assembly (CDSA) of crystalline-coil polyselenophene diblock copolymers represents a facile approach to nanofibers with distinct optoelectronic properties relative to those of their polythiophene analogs. The synthesis of an asymmetric diblock copolymer with a crystallizable, -conjugated poly(3-heptylselenophene) (P3C7Se) block and an amorphous polystyrene (PS) coblock is described. CDSA was performed in solvents selective for the PS block. Based on transmission electron microscopy (TEM) analysis, P3C7Se(18)-b-PS125 formed very long (up to 5 m), highly aggregated nanofibers in n-butyl acetate (nBuOAc) whereas shorter (ca. 500 nm) micelles of low polydispersity were obtained in cyclohexane. The micelle core widths in both solvents determined from TEM analysis (approximate to 8 nm) were commensurate with fully-extended P3C7Se(18) chains (estimated length = 7.1 nm). Atomic force microscopy (AFM) analysis provided characterization of the micelle cross-section including the PS corona (overall micelle width approximate to 60 nm). The crystallinity of the micelle cores was probed by UV-vis and photoluminescence (PL) spectroscopy and wide-angle X-ray scattering (WAXS).
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