Quinoidal structures incorporating expanded paraquinodimethane (p-QM) units have garnered great interest as functional organic electronic, optical, and magnetic materials. The direct use of the compact p-QM unit as an electronic building block, however, has been inhibited by the high reactivity conveyed by its biradical character. Herein, we introduce a stable p-QM variant, namely p-azaquinodimethane (p-AQM), that incorporates nitrogen atoms in the central ring and alkoxy substituents on the periphery to increase the stability of the quinoidal structure. The succinct synthesis from readily available precursors leads to regio-and stereospecific p-AQMs that can be readily integrated into the backbone of conjugated polymers. The quinoidal character of the p-AQM unit endows the resulting polymers with narrow band gaps and high carrier transport mobilities. The study of a series of copolymers employing different numbers of thiophene units revealed an unconventional trend in band gaps, which is distinct from the widely adopted donor−acceptor approach to tuning the band gaps of conjugated polymers. Theoretical calculations have shed light on the nature of this trend, which may provide a unique class of conjugated polymers with promising optical and electronic properties.

Three series of low-bandgap polymers based on a novel quinoidal paraazaquinodimethane (p-AQM) unit are devised and synthesized, enabling an in-depth study of the impact of structural factors such as polymer main chain, branching point of the side chain, and the length of the branch chains on the thin film morphologies and charge transport properties. Morphological studies reveal that the polymers composed of larger repeating units exhibit a stronger tendency to form edge-on lamella. On the other hand, altering the side chain structures of polymers with the same main chain configuration indicates that the branching point position has a more deterministic impact than the branch chain length on the interchain interactions and the crystallite orientation. These results demonstrate a compound odd-even effect of the branching point on the chain packing and morphology, which correlates well with the corresponding field effect transistor performances. The polymer with the branching point at the fourth carbon displays the highest charge carrier mobility over 1.0 cm 2 V −1 s −1 , concurrent with a bimodal texture. This study provides a comprehensive description of the correlations between polymer structures, thin film morphology, and device performances, providing a clear path to desirable bimodal thin film texture for charge transport.

The marriage of non-fullerene acceptors (NFAs) and ternary solar cell architecture has brought about great advances in organic photovoltaics. The primary effort, however, has been focusing on low-bandgap NFAs that exploit complementary absorption and energy-level cascade. Here we report a wide-bandgap NFA IDT-T that functions as an energy-level mediator, a fluorescence resonance energytransfer donor, an electron acceptor, and a crystallization modulator, which contribute synergistically in a ternary blend to yield high organic photovoltaic device performance.