Institute of Upconversion Nanoscale Materials, Henan Provincial Engineering Research Center of Green Anticorrosion Technology for Magnesium Alloy, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, People's Republic of China. Electronic address: [Email]
Accurate prediction on the up-conversion intersystem crossing rate (kUISC) is a critical issue for the molecular design of an efficient thermally activated delayed fluorescence (TADF) emitter, and the kUISC rate is considered to be mainly determined by the spin-orbit coupling matrix element (SOCME) and the singlet-triplet energy difference (∆EST). In the present contribution, we strategically designed a series of organic molecules, bearing an isoindole-dione core as the electron acceptor (A) unit and dinitrocarbazolyl, carbazolyl, diphenylcarbazolyl, dicarbazolyl and tercarbazolyl groups as the electron donor (D) units, respectively. Their SOCME and ∆EST values between the S1 and T1 states were calculated by the DFT and TD-DFT methodes, and the kUISC rates were estimated by using the semiclassical Marcus theory. The present studies indicate that as the π-conjugation in the D unit enhances, the ∆EST value gradually decreases, and the kUISC rate gradually increases. The molecule using tercarbazolyl as the D moiety is found to exhibit the largest kUISC in the present computations, as high as 1.22 × 106 s-1, which is of the same order of magnitude as an experimentally observed highly-efficient TADF emitter using a 4-benzoylpyridine as the A unit and the same tercarbazolyl group as the D moiety. The present results sufficiently prove the necessity of introducing strong electron-rich substituent groups when designing highly efficient TADF emitters.