Modulating Regioregularity of Poly(3-hexylthiophene)-based Amphiphilic Block Copolymers To Control Solution Assembly from Nanowires to Micelles

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In selective solvents, poly(3-hexylthiophene) (P3HT)-based block copolymers (BCPs) assemble into onedimensional nanowires (NWs) due to strong pi-pi stacking interactions of the P3HT block. Herein, we report the effect of P3HT regioregularity (RR) on the assembly of P3HTbased amphiphilic BCPs in solution. We synthesized a series of P3HT-block-poly(2-vinylpyridine) (P3HT-b-P2VP) copolymers with similar molecular weights and P3HT volume fractions but with different RRs, ranging from SS% to 95%, and studied their assembly in tetrahydrofuran/n-butanol mixtures. P3HT-b-P2VP copolymers with high RR (>80%) crystallized into well-ordered NWs with core widths consistent with fully extended P3HT chains. In BCP nanostructures with decreasing RR, more flexible P3HT chains produced gradual increases in the width of the NWs, from 12 to 24 nm. Eventually, a morphological transition to spherical micelle structures was observed at 55% RR The structural differences were visualized by incorporating Au nanoparticles, which locate at the interface of P3HT and P2VP blocks, onto the NWs and imaging the resulting hybrid nanostructures by transmission electron microscopy. In addition, the crystalline behaviors of the assembled nanostructures were determined using differential scanning calorimetry and grazing incidence X-ray scattering. We elucidated important relationships between the solution assembly behaviors and the crystalline interactions of conjugated semicrystalline-coil BCPs, which will guide design of future versatile BCP nanostructures.
Publisher
AMER CHEMICAL SOC
Issue Date
2018-11
Language
English
Article Type
Article
Citation

CHEMISTRY OF MATERIALS, v.30, no.21, pp.7912 - 7921

ISSN
0897-4756
DOI
10.1021/acs.chemmater.8b03510
URI
http://hdl.handle.net/10203/248279
Appears in Collection
CBE-Journal Papers(저널논문)
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