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Steric Switching for Thermally Activated Delayed Fluorescence by Controlling the Dihedral Angles between Donor and Acceptor in Organoboron Emitters.

Five emitters CzAZB, tBuCzAZB, tmCzAZB, dmAcAZB and PxzAZB based on dibenzo-1,4-azaborine as the electron acceptor and two identical amine groups as the donors were designed and synthesized. The dihedral angles between the planes of dibenzo-1,4-azaborine acceptor and amine-based donors greatly affect the thermally activated delayed fluorescence (TADF) property of these materials. A simple concept "steric switching" is introduced to predict whether the emitter possesses TADF property. CzAZB and tBuCzAZB, with very high photoluminescence quantum yields (PLQYs), but small dihedral angle, do not show TADF. In contrast, tmCzAZB reveals a PLQY of only 56% but with large dihedral angles due to the presence of the two methyl groups at C1 and C8 of the carbazole groups, the "steric switching" operates and the compound shows TADF property with deep-blue color having CIE coordinates of (0.14, 0.15). In a similar manner, dmAcAZB and PxzAZB with high PLQYs and with large dihedral angles between the donor and acceptor planes, the TADF "steric switching" readily operate to achieve device EQEs as high as 20.8 ±1.2% and 27.5 ±1.9% with blue and green emission, respectively.

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