Nitrogen-Bridged Fused-Ring Nonacyclic and Heptacyclic A-D-A Acceptors for Organic Photovoltaics.

In this work, we designed two nitrogen-bridged fluorene-based heptacyclic FNT and nonacyclic FNTT ladder-type structures, which were constructed by one-pot palladium-catalyzed Buchwald-Hartwig amination. FNT and FNTT were further end-capped by FIC acceptors to form two FNT-FIC and FNTT-FIC non-fullerene acceptors (NFAs), respectively. The two NFAs exhibit more red-shifted absorption and higher crystallinity compared to those of the corresponding carbon-bridged FCT-FIC and FCTT-FIC counterparts. Grazing incidence wide-angle X-ray scattering (GIWAXS) measurements reveal that the 2-butyloctyl groups on the nitrogen in the convex region of FNT-FIC interdigitate with the dioctyl groups on the fluorene in the concave region of another FNT-FIC, resulting in a lamellar packing structure with a spacing of 13.27 Å. As a consequence, the PM6:FNT-FIC (1:1 wt %) device achieved a power conversion efficiency (PCE) of only 6.60%, primarily due to the highly crystalline nature of FNT-FIC, which induced significant phase separation between PM6 and FNT-FIC in the blended film. However, FNTT-FIC, featuring 2-butyloctyl groups positioned on the nitrogen within the concave region of its curved skeleton, exhibits improved donor-acceptor miscibility, thereby promoting a more favorable morphology. As a result, the PM6:FNTT-FIC (1:1.2 wt %) device exhibited a higher PCE of 12.15% with an exceptional of 0.96 V. This research demonstrates that placing alkylamino moieties within the concave region of curved A-D-A NFAs leads to a better molecular design.