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The dimerization of small molecule acceptors (SMAs) holds significant potential by combining the advantages of both SMAs and polymer acceptors in realizing high power conversion efficiency (PCE) and operational stability in organic solar cells (OSCs). However, advancements in the selection and innovation of dimeric linkers are still challenging in enhancing their performance. In this study, three new dimeric acceptors, namely DY-Ar-4, DY-Ar-5, and DY-Ar-6 are synthesized, by linking two Y-series SMA subunits via an "end-to-end" strategy using flexible spacers (octyl, decyl, and dodecyl, respectively). The influence of spacer lengths on device performance is systematically investigated. The results indicate that DY-Ar-5 exhibits more compact and ordered packing, leading to an optimal morphology. OSCs based on PM6: DY-Ar-5 achieves a maximum PCE of 15.76%, attributes to enhance and balance carrier mobility, and reduce carrier recombination. This dimerization strategy using suitable non-conjugated linking units provides a rational principle for designing high-performance non-fullerene acceptors.
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