Developments in the Components of Metal‐Free Photoinitiated Organocatalyzed‐Atom Transfer Radical Polymerization (O‐ATRP)

Abstract The evolution of the atomic transfer radical polymerization (ATRP) has instigated an increased demand for designing versatile and tailored polymeric structures. However, the use of metal catalysts in traditional ATRP limits the use of polymers in many niche applications. The recent advancement in ATRP has engendered the substitution of metal‐catalysts by a more user‐friendly class of organic photoredox catalysts, which offer enhanced control over the polymerization reaction as these compounds can be easily activated and deactivated with just a source of light. These new photocatalysts have transformed the traditional ATRP to a metal‐free photoinitiated organocatalyzed – ATRP (O‐ATRP), which has potential applications in the medical and electronic sectors. This review covers the reductive and oxidative quenching mechanism of the metal‐free photoinduced O‐ATRP reaction and the function of each component to establish a successfully controlled polymerization reaction. The scope for each component has been encompassed in the study, which paves the way for future developments in the field.