Abstract
AbstractA series of 3‐substituted polythiophene copolymers having different side chain arrangements of hexyl and hexyloxy groups has been synthesized via the Grignard metathesis (GRIM) method and systematically studied. Despite differences in monomer reactivity ratios for the nickel‐catalyzed chain transfer polymerization, random sequences of hexyl‐ and hexyloxy‐substituted polythiophenes with different monomer compositions and adjustable band‐gap energies can be synthesized according to their respective comonomer feed ratio, as evidenced from NMR, UV, electrochemical measurements, and computational calculations. Structural characterization from X‐ray diffraction measurements reveals that the flexible hexyloxy side chains of the monomer significantly affect the crystallinity and molecular packing of the random copolymers. This study shows potential for synthesizing random copolymers with different monomer reactivities via the GRIM method for future optoelectronic applications. © 2014 Society of Chemical Industry
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