Controlling Energy Gaps of π‐Conjugated Polymers by Multi‐Fluorinated Boron‐Fused Azobenzene Acceptors for Highly Efficient Near‐Infrared Emission

Abstract We demonstrate that multi‐fluorinated boron‐fused azobenzene (BAz) complexes can work as a strong electron acceptor in electron donor‐acceptor (D‐A) type π‐conjugated polymers. Position‐dependent substitution effects were revealed, and the energy level of the lowest unoccupied molecular orbital (LUMO) was critically decreased by fluorination. As a result, the obtained polymers showed near‐infrared (NIR) emission ( λ PL =758–847 nm) with high absolute photoluminescence quantum yield ( Φ PL =7–23%) originating from low‐lying LUMO energy levels of the BAz moieties (−3.94 to −4.25 eV). Owing to inherent solid‐state emissive properties of the BAz units, deeper NIR emission ( λ PL =852980 nm) was detected in film state. Clear solvent effects prove that the NIR emission is from a charge transfer state originating from a strong D‐A interaction. The effects of fluorination on the frontier orbitals are well understandable and predictable by theoretical calculation with density functional theory. This study demonstrates the effectiveness of fluorination to the BAz units for producing a strong electron‐accepting unit through fine‐tuning of energy gaps, which can be the promising strategy for designing NIR absorptive and emissive materials.