Lessons learnt in photocatalysis - the influence of solvent polarity and the photostability of the photocatalyst.

Herein, we show that there is significant variation in both the triplet energies and redox properties of photocatalysts as a function of solvent based on a study of eight PCs in four solvents of varying polarity. A range of photocatalytic electron and energy transfer reactions were investigated using a subset of the PCs. For the photoredox reactions, the yields are not correlated with solvent polarity. Instead, when the PC could promote the formation of the target product, we observed photodegradation for all PCs across all solvents, something that is rarely investigated in the literature. This, therefore, makes it difficult to ascertain whether the parent PC and/or the photodegraded product is responsible for the photochemistry, or indeed, whether photodegradation is actually detrimental to the reaction yield. Conversely, the PCs were found to be photostable for energy transfer reactions; however, yields were not correlated to the triplet energies of the PCs, highlighting that triplet energies alone are not a suitable descriptor to discriminate the performance between PCs in photoinduced energy transfer processes.

Identification of the Key Parameters for Horizontal Transition Dipole Orientation in Fluorescent and TADF Organic Light-Emitting Diodes.

In organic light-emitting diodes (OLEDs), horizontal orientation of the emissive transition dipole moment (TDM) can improve light outcoupling efficiency by up to 50% relative to random orientation. Therefore, there have been extensive efforts to identify drivers of horizontal orientation. The aspect ratio of the emitter molecule and the glass-transition temperature (Tg ) of the films are currently regarded as particularly important. However, there remains a paucity of systematic studies that establish the extent to which these and other parameters control orientation in the wide range of emitter systems relevant for state-of-the-art OLEDs. Here, recent work on molecular orientation of fluorescent and thermally activated delayed fluorescent emitters in vacuum-processed OLEDs is reviewed. Additionally, to identify parameters linked to TDM orientation, a meta-analysis of 203 published emitter systems is conducted and combined with density-functional theory calculations. Molecular weight (MW) and linearity are identified as key parameters in neat systems. In host-guest systems with low-MW emitters, orientation is mostly influenced by the host Tg , whereas the length and MW of the emitter become more relevant for systems involving higher-MW emitters. To close, a perspective of where the field must advance to establish a comprehensive model of molecular orientation is given.