Herein, we report the synthesis and characterization of the first non-fullerene acceptor (NFA) containing a boron difluoride formazanate (<b>BF₂fz</b>) core end-capped with N-annulated perylene diimides (PDIs). Electronic coupling between the <b>BF₂fz</b> core and the PDI endcaps enabled tuning of the lowest unoccupied molecular orbital, leading to near-panchromatic optical absorption. Post-deposition solvent vapor annealing of the new NFA resulted in a significant

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... t in the optical spectra, which stretched into the near-IR. Proof-of-concept organic photovoltaic (OPV) devices were constructed to demonstrate the potential of this new material as an NFA. SVA treatment of the active layer resulted in a 2-fold increase in power conversion efficiency (PCE), due mainly to increases in the <b>BF₂PDI₂ </b>generated photocurrent that extended into the near-IR.