Bis‐Ortho‐Donor‐Modification of Boracyclic π‐Electron Systems beyond Steric Protection to Produce Thermally Activated Delayed Fluorescence Materials

Abstract Polycyclic π‐conjugated compounds that contain tricoordinate boron atoms at their periphery represent an attractive class of materials with electron‐accepting character. Their molecular design generally requires the introduction of a bulky aryl group onto the boron atom, where it provides predominantly kinetic stabilization. The addition of extra functionality to the aryl group on the boron atom can be expected to further expand the potential utility of this class of materials. Herein, we report the synthesis of a series of boracyclic π‐conjugated molecules with firm ortho B⋅⋅⋅N nonbonding interactions by introducing N‐containing electron‐donors at the ortho ‐positions of the aryl group on the boron atom. X‐ray crystallographic analysis revealed that the combination of a planar boracyclic π‐skeleton with only sp 2 carbons and a strong electron‐donating phenothiazine moiety results in a particularly short B⋅⋅⋅N distance. Theoretical study provided insights into the inherent nature of the B⋅⋅⋅N interaction. Owing to their donor–acceptor (D−A) structures, these molecules exhibit substantially red‐shifted fluorescence in solution, albeit that the fluorescence quantum yields ( Φ F ) are low. In contrast, when incorporated into films, these compounds exhibit thermally activated delayed fluorescence (TADF) with improved Φ F values. Organic light‐emitting diodes (OLEDs) fabricated using the ortho ‐donor‐substituted derivatives exhibit orange‐red electroluminescence.