Organocatalysed photoredox-mediated atom transfer radical polymerization (O-ATRP) is a very promising polymerization method as it eliminates concerns associated with transition-metal contamination of polymer products. However, reducing the amount of catalyst and expanding the monomer scope remain major challenges in O-ATRP. Herein, we report a systematic computer-aided-design strategy to identify powerful visible-light photoredox catalysts for O-ATRP. One of our discovered organic photoredox catalysts controls the polymerization of methyl methacrylate at sub-ppm catalyst loadings (0.5 ppm—a very meaningful amount enabling the direct use of polymers without a catalyst removal process); that is, 100–1,000 times lower loadings than other organic photoredox catalysts reported so far. Another organic photoredox catalyst with supra-reducing power in an excited state and high redox stability facilitates the challenging polymerization of the non-acrylic monomer styrene, which is not successful using existing photoredox catalysts. This work provides access to diverse challenging organic/polymer syntheses and makes O-ATRP viable for many industrial and biomedical applications.

有机催化的光氧化还原介导的原子转移自由基聚合（O-ATRP）是一种非常有前途的聚合方法，因为它消除了与聚合物产品的过渡金属污染相关的担忧。然而，减少催化剂的量和扩大单体范围仍然是O-ATRP的主要挑战。本文中，我们报告了系统的计算机辅助设计策略，以识别用于O-ATRP的强大的可见光光氧化还原催化剂。我们发现的一种有机光氧化还原催化剂可控制甲基丙烯酸甲酯在低于ppm的催化剂负载量（0.5 ppm，这是非常有意义的用量，无需催化剂去除过程即可直接使用聚合物）下的聚合反应；也就是说，负载量比迄今为止报道的其他有机光氧化还原催化剂低100-1,000倍。具有处于激发态的超还原能力和高氧化还原稳定性的另一种有机光氧化还原催化剂促进了非丙烯酸单体苯乙烯的具有挑战性的聚合，这不能使用现有的光氧化还原催化剂成功地进行。这项工作提供了获得具有挑战性的有机/聚合物合成的途径，并使O-ATRP在许多工业和生物医学应用中都可行。