Abstract
Thanks to their diversity, organic photocatalysts (PCs) have been widely used in manufacturing polymeric products with well-defined molecular weights, block sequences, and architectures. Still, however, more universal property-performance relationships are needed to enable the rational design of such PCs. That is, a set of unique descriptors ought to be identified to represent key properties of the PCs relevant for polymerisation. Previously, the redox potentials of excited PCs (PC(*)) were used as a good descriptor for characterising very structurally similar PCs. However, it fails to elucidate PCs with diverse chromophore cores and ligands, among which those used for polymerisation are a good representative. As showcased by model systems of organocatalysed atom transfer radical polymerisation (O-ATRP), new universal descriptors accounting for additional factors, such as the binding and density overlap between the PC(*) and initiator, are proposed and proved to be successful in elucidating the experimental performances of PCs in polymerisation. While O-ATRP is exemplified here, the approach adopted is general for studying other photocatalytic systems.