The true structure of alternating conjugated polymers – the state-of-the-art materials for a number of organic electronics technologies – often deviates from the idealized picture but this gets relatively limited attention. Here, we quantify the amount of homocoupling defects resulting from Stille polymerization and shed new light on the actual distribution of these structural defects in a prototype polymer material. Further, when compared to a homocoupling-free variant, these defects hinder fullerene intercalation, with a clear implication on charge-transfer absorption. This demonstrates that molecular defects may (strongly) impact polymer and blend properties and calls for increased attention for defect-free materials.
Semiconducting organic polymers are most often synthesized by linking an electron poor and an electron rich (hetero)aromatic building block via a transition metal catalyzed cross-coupling copolymerization. Researchers aiming at exploring applications and fundamental performance limits, for example for organic photovoltaics, organic photodetectors, and organic electrochemical transistors, often assume that the obtained material consists strictly of a perfect repetition of the depicted polymeric repeating unit, whereas this is likely not the case. In this contribution, we demonstrate a synthesis approach to obtain the depicted “perfect” structure of these types of polymers and the influence of material defects on the optoelectronic properties and device performance.
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