Metal‐Free Organocatalyzed Atom Transfer Radical Polymerization: Synthesis, Applications, and Future Perspectives

Reversible deactivation radical polymerization (RDRP) is a class of powerful techniques capable of synthesizing polymers with a well-defined structure, properties, and functionalities. Among the available RDRPs, ATRP is the most investigated. However, the necessity of a metal catalyst represents a drawback and limits its use for some applications. O-ATRP emerged as an alternative to traditional ATRP that uses organic compounds that catalyze polymerization under light irradiation instead of metal. The friendly nature and the robustness of O-ATRP allow its use in the synthesis of tailorable advanced materials with unique properties. In this review, the fundamental aspects of the reductive and oxidative quenching mechanism of O-ATRP are provided, as well as insights into each component and its role in the reaction. Besides, the breakthrough recent studies that applied O-ATRP for the synthesis of functional materials are presented, which illustrate the significant potential and impact of this technique across diverse fields.