In series-connected tandem organic solar cells (TOSCs), various light-harvesting molecules with complementary absorptions are explored with the aim of collaboratively utilizing solar light to the maximum extent. In sharp contrast to the small molecular acceptors that possessing almost the successively tunable bandgaps, high-performance wide-bandgap (WBG) polymer donors in TOSCs are quite scarce, with only PM6 (optical bandgaps, Egopt = 1.80 eV) and D18 (Egopt = 1.98 eV) being widely used. Herein, to develop WBG polymer donors with large open-circuit voltages (VOC) and high-energy photon absorption, two pyrazinyl polymer donors, PPy1 and PPy2, are synthesized with branched 2-butyloctyl and n-dodecyl chains on polymeric backbones, respectively, demonstrating the downshifted highest occupied molecular orbital energy levels of approximate to-5.60 eV and thus afford Egopt over 2.0 eV. Consequently, when blending with a WBG acceptor F-ThCl, PPy2:F-ThCl-based devices exhibit a higher power conversion efficiency (PCE) of 14.50% and fill factor of 77.66%. In light of its large VOC of 1.07 V, TOSCs based on PPy2 are further fabricated and exhibit an impressive PCE of 19.35% by using a narrow bandgap blend of PM6:CH1007:F-2F as a rear cell. This work demonstrates the great potential of pyrazine units in constructing WBG polymer donors for achieving record-breaking TOSCs.

Two pyrazinyl polymer donors of PPy1 and PPy2 are constructed, demonstrating the optical bandgaps over 2.0 eV. Due to stronger self-aggregation property and enhanced dielectric feature, PPy2:F-ThCl based organic solar cells show a good efficiency of 14.50%. In light of its large open-circuit voltage of 1.07 V, tandem devices are further fabricated and exhibit an impressive PCE of 19.35%.