Designing near-infrared (NIR) absorbing donor–acceptor (D–A) polymers with photoresponse beyond 900 nm has remained a challenge in the area of organic photovoltaics (OPV) owing to the limited kinds of strong electron acceptors.

Manipulating the electron deficiency and controlling the regioregularity of π-conjugated polymers are important for the fine-tuning of their electronic and electrochemical properties to make them suitable for an organic solar cell. Here, we report such a molecular design of unsymmetric diketopyrrolopyrrole (DPP) based copolymers with different aromatic side units of either thiophene (Th), pyridine (Py), or fluorobenzene (FBz). The unsymmetric electron acceptors of Th–DPP–Py and Th–DPP–FBz were polymerized with the electron donor of two-dimensional benzobisthiophene (BDT-Th), affording two regiorandom DPP copolymers. They exhibited contrasting molecular orbital levels and bulk heterojunction morphology in methanofullerene-blended films, leading to power conversion efficiencies of 3.75 and 0.18%, respectively. We further synthesized a regioregular DPP copolymer via sandwiching the centrosymmetric BDT-Th unit by two Th–DPP–Py units in an axisymmetric manner. The extensive characterization through morphology observation, X-ray diffraction, and space-charge-limited current mobilities highlight the case-dependent positive/negative effects of regioregularity and electron deficiency control.

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