Abstract
Three pyromellitic diimide(PMDI)‐based polymers—poly(pyromellitic diimide‐co‐bithiophene) [poly(PMDI‐BTh)], poly(pyromellitic diimide‐co‐tetrathiophene) [poly(PMDI‐TTh)], and poly(pyromellitic diimide‐co‐benzodithio‐ phene) [poly(PMDI‐BDTTh)]—are synthesized to study the influence of different thiophene‐containing electron‐donating groups on the crystallizability of PMDI‐based conjugated polymers. Computer simulation using Density Functional Theory (DFT) [Gaussian B3LYP/6–31 + G(d,p)] indicates that poly(PMDI‐BDTTh) has a more planar molecular structure than the other two copolymers. Powder XRD diffraction experiment of the poly(PMDI‐BDTTh) shows a diffraction peak at about 2θ = 6.0°, but no diffraction peak occurs for poly(PMDI‐BTh) and poly(PMDI‐TTh). Although PMDI is a planar structure that is favorable for the molecular aggregation, a comonomer with planar structure seems to be very crucial in order to synthesize a crystallizable push–pull‐type PMDI‐based conjugated copolymer.
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