Impact of secondary donor units on the excited-state properties and thermally activated delayed fluorescence (TADF) efficiency of pentacarbazole-benzonitrile emitters

The performance of organic light-emitting diodes based on thermally activated delayed fluorescence emitters depends on the efficiency of reverse intersystem crossing (RISC) processes, which are promoted by a small energy gap between the lowest singlet (S1) and triplet (T1) excited states and large spin–orbit couplings. Recently, it was proposed that the introduction of secondary donor units into 2,3,4,5,6-penta(9H-carbazol-9-yl)benzonitrile (5CzBN) can significantly increase the mixing between triplet states with charge-transfer (CT) and local-excitation characteristics and consequently increase the spin–orbit couplings. Here, the results of long-range corrected density functional theory calculations show that the main impact on the RISC rates of substituting 5CzBN with secondary donors is due to a decrease in adiabatic singlet–triplet energy gaps and intramolecular reorganization energies rather than to a change in spin–orbit couplings. Our calculations underline that at least two singlet and three triplet excited states contribute to the ISC/RISC processes in 5CzBN and its derivatives. In addition, we find that in all emitters, the lowest singlet excited-state potential energy surface has a double-minimum shape.