In Silico Screening and Experimental Verification of Near‐Infrared‐Emissive Two‐Boron‐Doped Polycyclic Aromatic Hydrocarbons

Embedding two boron atoms into a polycyclic aromatic hydrocarbon (PAH) leads to the formation of a neutral analogue that is isoelectronic to the corresponding dicationic PAH skeleton, which can significantly alter its electronic structure. Based on this concept, we explore herein the identification of near‐infrared (NIR)‐emissive PAHs with the aid of an in silico screening method. Using perylene as the PAH scaffold, we embedded two boron atoms and fused two thiophene rings to it. Based on this design concept, all possible structures (ca. 2500 entities) were generated using a comprehensive structure generator. Time‐dependent DFT calculations were conducted on all these structures, and promising candidates were extracted based on the vertical excitation energy, transition dipole moment, and atomization energy per bond. One of the extracted dithieno‐diboraperylene candidates was synthesized and indeed exhibited emission at 724 nm with a quantum yield of 0.40 in toluene, demonstrating the validity of this screening method. This modification was further applied to other PAHs, and a series of thienobora‐modified PAHs was synthesized. An in silico screening method based on a comprehensive structure generation followed by TD‐DFT calculations was established for developing near‐infrared (NIR) emissive polycyclic aromatic hydrocarbons. Using perylene as a scaffold, a two‐boron‐doping/two‐thiophene‐fusion strategy was applied to provide ca. 2500 possible structures. One of the promising candidates, extracted using several criteria, was synthesized and exhibited intense NIR‐emission.