Benzodifluoranthenes and Their π‐Extended Derivatives: Syntheses, Structural Analyses, Properties, and Hole Mobilities

New classes of arenes, benzo[1,2‐ b :5,4‐ b′ ]difluoranthene ( syn ‐B b D), benzo[1,2‐ b :4,5‐ b′ ]difluoranthene ( anti ‐B b D) and their π‐extended derivatives, were regioselectively synthesized by rhodium‐catalyzed intramolecular annulations of bis[2‐(arylethynyl)phenyl]‐substituted linear [3]phenylenes and biphenyleno[2,3‐ b ]biphenylenes, respectively. The structures and molecular stacking of these compounds were verified by X‐ray crystallography. Notably, bis(4‐ n ‐butylphenyl)‐substituted anti ‐B b D ( 2b ), characterized by a reorganization energy of 164 meV, organizes into either 2D “brickwork” or 1D slipped stacking motifs. These architectures facilitate robust electronic coupling integrals of 84 and 108 meV, respectively, which profoundly dictate the material's charge‐transport dynamics. Solution‐processed organic field‐effect transistors (OFETs) based on 2b exhibited an exceptional hole mobility of 3.43 cm 2 V −1 s −1 , consistent with leading as‐cast, solution‐processed small‐molecule semiconductors. This work not only establishes B b Ds as a promising class of high‐performance semiconductors but also elucidates pivotal design paradigms for future solution‐processable materials that form a critical connection between molecular topology, supramolecular aggregation, and charge‐transport efficiency.