Dihedral Angle Control of Blue Thermally Activated Delayed Fluorescent Emitters through Donor Substitution Position for Efficient Reverse Intersystem Crossing

This study shows a molecular design strategy for controlling the dihedral angle of two carbazole donors linked to a 2,4-diphenyl-1,3,5-triazine acceptor by a phenyl unit. Using this approach, six thermally activated delayed fluorescence emitters were synthesized with donors placed in various positions around a central phenyl core, and the photophysical relationship between the donor position and its dihedral angle was investigated. We demonstrate that this angle can affect both the strength of the charge transfer state and the conjugation across the entire molecule, effectively changing the singlet–triplet energy gap of the system. We conclude that materials containing two substituted −ortho donors or one −ortho and an adjacent −meta have the smallest energy gaps and the shortest delayed fluorescence lifetimes. On the other hand, emitters with no −ortho substituted donors have larger energy gaps and slow-to-negligible delayed fluorescence. When applying these materials to organic light-emitting diodes, these blue-emitting devices have a range of electrical properties, the best producing efficiencies as high as 21.8% together with high resistance to roll-off that correlate with the reverse intersystem crossing rates obtained