Constructing Multiresonance Thermally Activated Delayed Fluorescence Emitters for Organic LEDs: A Computational Investigation.

Multiple resonance thermally activated delayed fluorescence (MR-TADF) materials have acquired substantial attention due to their high electroluminescence efficiency with narrow emission spectra. However, the existing MR-TADF emitters suffer from substantial efficiency roll-off due to insufficient rate constants of the reverse intersystem crossing ( k RISC ) process compared to the traditional TADF materials. Herein, we employ the DLPNO-STEOM-CCSD method, which is computationally less expensive than the wave function-based EOM-CCSD method, to evaluate the electronic and photophysical properties of MR-TADF materials accurately. The predicted singlet-triplet energy gap (Δ E ST ), one of the critical parameters governing the TADF efficiency, exhibits remarkable agreement with the experimental measurement, with a standard deviation value of 0.026 eV (obtained based on five experimentally synthesized MR-TADF systems). The proposed technique was utilized to determine the suitability of 15 newly designed MR-TADF emitters via their computed radiative and nonradiative rates, luminescence efficiencies, and exciton characteristics. Moreover, most conceived molecules exhibit blue emission with decent to strong oscillator strengths, making them potential candidates for practical light-emitting applications. The proposed computational route will undoubtedly accelerate the designing and prescreening of potential MR-TADF emitters before their expensive laboratory synthesis and characterization.