![]() Tyrian Purple (6,6′-dibromoindigo, 5) is a naturally occurring dye of significant legacy. The benzene rings of the indigo dye are not involved in the conjugation of the IND unit and offer the potential to introduce cross-conjugation. INDs are formed through a dual condensation-annulation reaction of indigo and an aromatic acetyl chloride. These materials with fully conjugated non-planar backbones exhibited narrow optical band gaps (∼1.2 eV), gave high power conversion efficiencies in OPVs (up to 4.1%), and gave high performance charge transport in OFETs for holes and electrons up to 1.0 and 3.1 cm 2 V −1 s −1 respectively. Our recent work on conjugated organic polymers exploiting the relatively unexplored building block indolonaphthyridine (IND) was inspired by the chromophore of natural indigo dye. 7 Other common building blocks have been exploited in cross-conjugated polymers including isoindigo, 8,9 fluorene, 10–13 carbazole, 14 and some more atypical systems, 15–20 however successful application in devices is rarely reported. reported high hole mobilities in diketopyrrolopyrrole (DPP) based cross-conjugated polymers. demonstrated the first successful use of a thienothiophene cross-conjugated polymer as a p-type OFET material, exhibiting hole transport up to 0.05 cm 2 V −1 s −1. Due to their shorter effective conjugation lengths, cross-conjugated polymers typically have wider band gaps and increased ionisation potentials, making them more stable to oxidative doping when operated in air. 1–3Ī design approach which has seldom been investigated is the interruption of conjugation along a polymer backbone. The most widely employed strategy for band gap engineering is in alternating donor–acceptor (D–A) copolymers, where the energy of the highest occupied molecular orbital (HOMO) is typically dictated by the donor unit whilst the energy of the lowest unoccupied molecular orbital (LUMO) is dictated by the acceptor. Their effectiveness as donor materials in the bulk heterojunction of organic photovoltaics (OPVs) and in transporting charge carriers in organic field-effect transistors (OFETs) is reliant on the energetic tailoring of frontier molecular orbital (MO) energy levels and thus the band gap between them. ![]() ![]() Introduction Organic semiconducting polymers have received large attention in the past two decades due to their low cost, mechanical flexibility, and ease of processing. Quantum chemical calculations provide insight into this behaviour, suggesting that, whilst conjugation along the HOMO is indeed inhibited via molecular design, these materials possess highly delocalized LUMOs, facilitating high n-type charge transport. The cross-conjugated polymers exhibited relatively high n-type charge transport performance in organic field-effect transistors, a rare characteristic for this type of polymer. By employing cross-conjugation within the polymer backbone as a synthetic strategy, we are able to engineer optical gaps such that the novel materials absorb over the entire visible spectrum. ![]() Herein, we present two novel organic semiconducting polymers synthesised from an ancient dye.
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