Intramolecular locking and coumarin insertion: a stepwise approach for TADF design

Abstract

Three novel TADF (thermally activated delayed fluorescence) emitters based on the well-studied Qx-Ph-DMAC fluorophore are designed and synthesized. The photophysical properties of these materials are studied from a theoretical and experimental point of view, demonstrating the cumulative effects of multiple small modifications that combine to afford significantly improved TADF performance. First, an extra phenyl ring is added to the acceptor part of Qx-Ph-DMAC to increase the conjugation length, resulting in BQx-Ph-DMAC, which acts as an intermediate molecular structure. Next, an electron-deficient coumarin unit is incorporated to fortify the electron accepting ability, affording ChromPy-Ph-DMAC with red-shifted emission. Finally, the conjugated system is further enlarged by 'locking' the molecular structure, generating DBChromQx-DMAC with further red-shifted emission. The addition of the coumarin unit significantly impacts the charge-transfer excited state energy levels with little effect on the locally excited states, resulting in a decrease of the singlet-triplet energy gap. As a result, the two coumarin-based emitters show considerably improved TADF performance in 1 w/w% zeonex films when compared to the initial Qx-Ph-DMAC structure. 'Locking' the molecular structure further lowers the singlet-triplet energy gap, resulting in more efficient reverse intersystem crossing and increasing the contribution of TADF to the total emission. Starting from the known emitter Qx-Ph-DMAC, stepwise modification by coumarin integration and locking of the acceptor affords closer alignment of excited states, leading to improvements in TADF performance and emission efficiency in DBChromQx-DMAC.