Precise Methylation Yields Acceptor with Hydrogen‐Bonding Network for High‐Efficiency and Thermally Stable Polymer Solar Cells

Utilizing intermolecular hydrogen-bonding interactions stands for an effective approach in advancing the efficiency and stability of small-molecule acceptors (SMAs) for polymer solar cells. Herein, we synthesized three SMAs (Qo1, Qo2, and Qo3) using indeno1,2-bquinoxalin-11-one (Qox) as the electron-deficient group, with the incorporation of a methylation strategy. Through crystallographic analysis, it is observed that two Qox-based methylated acceptors (Qo2 and Qo3) exhibit multiple hydrogen bond-assisted 3D network transport structures, in contrast to the 2D transport structure observed in gem-dichlorinated counterpart (Qo4). Notably, Qo2 exhibits multiple and stronger hydrogen-bonding interactions compared with Qo3. Consequently, PM6 : Qo2 device realizes the highest power conversion efficiency (PCE) of 18.4 %, surpassing the efficiencies of devices based on Qo1 (15.8 %), Qo3 (16.7 %), and Qo4 (2.4 %). This remarkable PCE in PM6 : Qo2 device can be primarily ascribed to the enhanced donor-acceptor miscibility, more favorable medium structure, and more efficient charge transfer and collection behavior. Moreover, the PM6 : Qo2 device demonstrates exceptional thermal stability, retaining 82.8 % of its initial PCE after undergoing annealing at 65 °C for 250 hours. Our research showcases that precise methylation, particularly targeting the formation of intermolecular hydrogen-bonding interactions to tune crystal packing patterns, represents a promising strategy in the molecular design of efficient and stable SMAs.