Fluorescence via Reverse Intersystem Crossing from Higher Triplet States in a Bisanthracene Derivative

Abstract: To elucidate the high external quantum efficiency observed for organic light-emitting diodes using a bisanthracene derivative, BD1, as the emitting molecule, off-diagonal vibronic coupling constants (VCCs) between the excited states of BD1, which govern non-radiative transition rates, were calculated employing time-dependent density functional theory. The VCCs were analysed based on the concept of vibronic coupling density. The VCC calculations suggest a fluorescence via higher triplets (FvHT) mechanism, which entails the conversion of a T$_4$ exciton generated during electrical excitation into an S$_2$ exciton via reverse intersystem crossing (RISC); moreover, the S$_2$ exciton relaxes to a fluorescent S$_1$ exciton because of large vibronic coupling between S$_2$ and S$_1$. This mechanism is valid as long as the relaxation of triplet states higher than T$_1$ to lower states is suppressed. The symmetry-controlled thermally activated delayed fluorescence (SC-TADF) and inverted singlet and triplet (iST) structure, which have been proposed in our previous studies, are the special examples of the FvHT mechanism that need high molecular symmetry. However, BD1 achieves the FvHT mechanism in spite of its asymmetrical structure. A general condition for the suppression of radiative and non-radiative transitions in molecules with pseudo-degenerate electronic structures such as BD1 is discussed. A superordinate concept, fluorescence via RISC, which includes TADF, SC-TADF, iST structure, and FvHT is also proposed.