Shedding light on thermally-activated delayed fluorescence.

Thermally activated delayed fluorescence (TADF) is a hot research topic in view of its impressive applications in a wide variety of fields from organic LEDs to photodynamic therapy and metal-free photocatalysis. TADF is a rare and fragile phenomenon that requires a delicate equilibrium between tiny singlet-triplet gaps, sizable spin-orbit couplings, conformational flexibility and a balanced contribution of charge transfer and local excited states. To make the picture more complex, this precarious equilibrium is non-trivially affected by the interaction of the TADF dye with its local environment. The concurrent optimization of the dye and of the embedding medium is therefore of paramount importance to boost practical applications of TADF. Towards this aim, refined theoretical and computational approaches must be cleverly exploited, paying attention to the reliability of adopted approximations. In this perspective, we will address some of the most important issues in the field. Specifically, we will critically review theoretical and computational approaches to TADF rates, highlighting the limits of widespread approaches. Environmental effects on the TADF photophysics are discussed in detail, focusing on the major role played by dielectric and conformational disorder in liquid solutions and amorphous matrices.