| Summary: | The B←N is isoelectronic to the C−C, with the former having stronger dipole moment and higher electron affinity. Replacing the C−C bonds in conjugated polymers with B←N bonds is an effective pathway toward novel polymers with strong electron affinity and adjustable optoelectronic properties. In this work, we synthesize a conjugated copolymer, namely, BNIDT-DPP, based on a B←N embedded unit, BNIDT, and a typical electron-deficient unit, diketopyrrolopyrrole (DPP). For comparison, the C−C counterpart, i.e., IDT-DPP, is also synthesized. In contrast to IDT-DPP, the B←N embedded polymer BNIDT-DPP shows an extended absorption edge (836 versus 978 nm), narrowed optical bandgap (1.48 versus 1.27 eV), and higher electron affinity (3.54 versus 3.74 eV). The Gaussian simulations reveal that the B←N embedded polymer BNIDT-DPP is more electron-deficient in contrast to IDT-DPP, supporting the decreased bandgap and energy levels of BNIDT-DPP. Organic thin-film transistor (OTFT) tests indicate a well-defined p-type characteristic for both IDT-DPP and BNIDT-DPP. The hole mobilities of IDT-DPP and BNIDT-DPP tested by OTFTs are 0.059 and 0.035 cm<sup>2</sup>/V·s, respectively. The preliminary fabrication of all-polymer solar cells based on BNIDT-DPP and PBDB-T affords a PCE of 0.12%. This work develops a novel B←N embedded polymer with strong electron affinity and extended absorption, which is potentially useful for electronic device application.
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