Fiber-Like Micelles from the Crystallization-Driven Self-Assembly of Poly(3-heptylselenophene)-block-Polystyrene

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 crystall...

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Bibliographic Details
Published in:Macromolecular chemistry and physics 2015-03, Vol.216 (6), p.685-695
Main Authors: Kynaston, Emily L., Gould, Oliver E. C., Gwyther, Jessica, Whittell, George R., Winnik, Mitchell A., Manners, Ian
Format: Article
Language:English
Subjects:
Block copolymers
conjugated polymers
Crystal structure
Crystallization
living polymerization
Micelles
Microscopes
Microscopy
Nanofibers
Polystyrene resins
Self assembly
Solvents
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Summary: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, π‐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, P3C7Se18‐b‐PS125 formed very long (up to 5 μm), 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 (≈ 8 nm) were commensurate with fully‐extended P3C7Se18 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 ≈ 60 nm). The crystallinity of the micelle cores was probed by UV–vis and photoluminescence (PL) spectroscopy and wide‐angle X‐ray scattering (WAXS). Polyselenophene block copolymers: a synthetic route to crystalline‐coil diblock copolymers with a crystallizable poly(3‐heptylselenophene) (P3C7Se) block and an amorphous polystyrene (PS) coblock is outlined via a Cu‐catalyzed, azide–alkyne click method. Crystallization‐driven self‐assembly (CDSA) in block‐selective solvents leads to the formation of nanofibers with a crystalline P3C7Se core and a solvent‐swollen PS corona.
ISSN:1022-1352
1521-3935
DOI:10.1002/macp.201400541