Dipyrrole-Fused Naphthalene Diimide as a Building Block for High-Performance Organic Semiconductors

High Resolution Image Download MS PowerPoint Slide Core annulation of naphthalene diimide (NDI) represents a powerful strategy to modulate its electronic structure and solid-state organization. Here, we report the first pyrrole-fused NDI (NDPI) framework and elucidate its structural and electronic characteristics. Single-crystal X-ray diffraction reveals a highly planar π-core with short π–π stacking distance (3.33 Å) and strong intermolecular N–H···O hydrogen bonding (2.07 Å), highlighting the unique supramolecular features introduced by pyrrole annulation. Building on this motif, a series of donor–acceptor polymers was synthesized and systematically evaluated in OFET devices. The polymers exhibit optical bandgaps of 1.32–1.39 eV. Device mobilities range from 0.10 to 0.59 cm 2 V –1 s –1, with charge transport behavior tunable from balanced ambipolar to unipolar n-type depending on donor strength. Correlation of AFM and GIWAXS analyses suggests that charge mobility is governed not solely by crystallinity, but by the interplay between π–π stacking and domain connectivity. This work establishes NDPI as a versatile building block for high-performance organic semiconductors.