| Summary: | The molecular design of a wide-bandgap polymer donor is critical to achieve high-performance organic photovoltaic devices. Herein, a new dibenzo-fused quinoxalineimide (BPQI) is successfully synthesized as an electron-deficient building block to construct donor–acceptor (D–A)-type polymers, namely P(BPQI-BDT) and P(BPQI-BDTT), using benzodithiophene and its derivative, which bears different side chains, as the copolymerization units. These two polymers are used as a donor, and the narrow bandgap (2,20-((2Z,20Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo [3,4-e]thieno[2,″30′:4′,50]thieno[20,30:4,5]pyrrolo[3,2g]thieno[20,30:4,5]thieno[3,2-b]indole-2,10 diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) Y6 is used as an acceptor to fabricate bulk heterojunction polymer solar cell devices. Y6, as a non-fullerene receptor (NFA), has excellent electrochemical and optical properties, as well as a high efficiency of over 18%. The device, based on P(BPQI-BDTT):Y6, showed power conversion efficiencies (PCEs) of 6.31% with a <i>J</i><sub>SC</sub> of 17.09 mA cm<sup>−2</sup>, an open-circuit voltage (<i>V</i><sub>OC</sub>) of 0.82 V, and an FF of 44.78%. This study demonstrates that dibenzo-fused quinoxalineimide is a promising building block for developing wide-bandgap polymer donors.
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