Journal
MACROMOLECULES
Volume 56, Issue 5, Pages 1875-1883Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.2c01943
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In this study, optically active pi-conjugated block copolymers consisting of polyfluorene and poly(phenyl isocyanide) were synthesized in one pot through two sequential polymerizations. The resulting copolymers self-assembled into single-handed helical nanofibers, exhibiting excellent optical activity and circularly polarized luminescence properties.
Optically active pi-conjugated block copolymers are of considerable significance and interest, but their controlled synthesis and helical self-assembly remain challenging. In this study, pi-conjugated block copolymers consisting of polyfluorene (PF) and poly(phenyl isocyanide) (PPI) segments were facilely prepared in one pot through two sequential polymerizations. First, a Pd(II)-terminated PF precursor was synthesized via the Suzuki cross-coupling polymer-ization of 7-bromo-9,9-dihexylfluorene-2-boronic acid pinacol ester, which was catalyzed using a Pd(0)/t-Bu3P system. Then, PF-b-PPI copolymers with controlled molar mass and narrow dispersities were fabricated via controlled polymerization of phenyl isocyanide monomers utilizing Pd(II)-terminated PF as the catalyst. Benefiting from the pi-conjugated structure of the PF block and the helicity of the PPI block, the resulting PF-b-PPI copolymers could self-assemble into single-handed helical nanofibers. In the self-assembly process, chirality was transferred from the helical PPI block to the self-assembled helical nanofibers, thereby endowing them with optical activity and excellent circularly polarized luminescence properties.
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