Photoinitiated polymerization has been the subject of continued research efforts due to the numerous applications in which this polymerization technique is involved (coatings, inks, adhesives, optoelectronic, laser imaging, stereolithography, nanotechnology, etc.). More recently, photopolymerization has received renewed interest due to the emergence of 3D-printing technologies. However, despite current academic and industrial interest in photopolymerization methodologies, a major limitation lies in the slow rates of photopolymerization. The development of new photoinitiating systems aimed at addressing this limitation is an active area of research. Photopolymerization occurs through the exposure of a curable formulation to light, generating radical and/or cationic species to initiate polymerization. At present, photopolymerization is facing numerous challenges related to safety, economic and ecological concerns. Furthermore, practical considerations such as the curing depth and the competition for light absorption between the chromophores and other species in the formulation are key parameters drastically affecting the photopolymerization process. To address these issues, photoinitiating systems operating under low intensity visible light irradiation, in the absence of solvents are highly sought after. In this context, the use of photoredox catalysis can be highly advantageous; that is, photoredox catalysts can provide high reactivities with low catalyst loading, permitting access to high performance photoinitiating systems. However, to act as efficient photoredox catalysts, specific criteria have to be fulfilled. A strong absorption over the visible range, an ability to easily oxidize or reduce as well as sufficient photochemical stability are basic prerequisites to make these molecules desirable candidates for photoredox catalysis. Considering the similarity of requirements between organic electronics and photopolymerization, numerous materials initially designed for applications in organic electronics have been revisited in the context of photopolymerization. Organic electronics is a branch of electronics and materials science focusing on the development of semiconductors devoted to three main research fields; organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs), and organic solar cells (OSCs). The contribution of organic electronics to the field of electronics is important as it paves the way toward cheaper, lighter, and more energy efficient devices. In the present context of photopolymerization, materials that were investigated as photocatalysts were indifferently organic semiconductors used for transistors, charge-transport materials, and light-emitting materials used in electroluminescent devices or conjugated polymers and small molecule dyes for solar cells. In this Account, we summarize our latest developments in elaborating on photocatalytic systems based on these new classes of compounds. Through an in-depth understanding of the parameters governing their reactivities and our efforts to incorporate these materials into photoinitiating systems, we provide new knowledge and a valuable insight for future prospects.
