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Three low-band-gap copolymers based on isoindigo acceptor units were designed and successfully synthesized by direct arylation polycondensation method. Two of them were benzodithiophene (BDT)-isoindigo copolymers ( PBDTI-OD  and  PBDTI-DT ) with 2-octlydodecyl (OD) and 2-decyltetradecyl (DT) substituted isoindigo units, respectively. Thiophene donor and DT-substituted isoindigo acceptor units were copolymerized to synthesize  PTI-DT . The copolymers have a broad absorption range that extends to over 760 nm with a band gap ≈1.5 eV. The photophysical property studies showed that the BDT-based copolymers have non-polar ground states. Their emission exhibited the population of the intramolecular charge transfer (ICT) state in polar solvents and tightly bound excitonic state in non-polar solvents due to self-aggregation. On the contrary, the emission from the thiophene-based copolymers was only from the tightly bound excitonic state. The thermal decomposition temperature of the copolymers was above 380 °C. The X-ray diffraction pattern of the three copolymers showed a halo due toπ  −  πstacking. A second, sharper peak was observed in the BDT-based copolymer with a longer side chain on the isoindigo unit ( PBDTI-DT ), and the thiophene-based copolymers with  PTI-DT , exhibiting a better structural order.

polymers

Photophysical, Thermal and Structural Properties of Thiophene and Benzodithiophene-Based Copolymers Synthesized by Direct Arylation Polycondensation Method