Cyano Decoration of -Bridge to Boost Photoluminescence and Electroluminescence Quantum Yields of Triazine/Carbazole Based Blue TADF Emitter

In general, a large donor-acceptor dihedral angle is required to guarantee sufficient frontier molecular orbitals separation for thermally activated delayed fluorescence (TADF) emitters, which is intrinsically unfavorable for the radiative transition. We present a molecular design method favoring both reverse intersystem crossing (RISC) and radiative transitions even at a moderate D-A angle. A blue TADF emitter TrzBuCz-CN was designed with triazine/tert-butylcarbazole as donor/acceptor and cyano (CN) incorporated on the phenylene bridge. In comparison with the methyl decoration in similar way (TrzBuCz-Me), CN decoration reduced the D-A dihedral angle from 70 degrees to 60 degrees, which is intrinsically not favorable for sufficient FMO separation, but unexpectedly reduced the singlet and triplet energy gap (Delta EST) and thus facilitated TADF feature by pulling down the lowest singlet state energy. While the reduced distorsion instead improved the HOMO-LUMO overlap and boosted the fluorescence quantum yield from 41 % to 94 %. The blue organic light-emitting diode of TrzBuCz-CN exhibited an external quantum efficiency of 13.7 % with emission peak at 466 nm, greatly superior to 6.0 % of TrzBuCz-Me. The result provides a feasible design strategy to facilitate both RISC and radiation processes by CN decoration of the linking bridge of TADF emitters. Incorporating less bulky cyano group to replace methyl on pi bridge of donor-pi-acceptor molecule instead strengthened the thermally activated delayed fluorescence feature through enhancing intramolecular charge transfer, and boosted photoluminescence quantum yield from 40 % to 94 % by increasing HOMO-LUMO overlap, finally led to an EQE of 14 % in blue OLED.image