Development of photocatalysts (PCs) with diverse properties has been essential in the advancement of organocatalyzed atom transfer radical polymerization (O-ATRP). Dimethyl dihydroacridines are presented here as a new family of organic PCs, for the first time enabling controlled polymerization of challenging acrylate monomers by O-ATRP. Structure-property relationships for seven PCs are established, demonstrating tunable photochemical and electrochemical properties, and accessing a strongly oxidizing 2 PC.+ intermediate for efficient deactivation. In O-ATRP, the combination of PC, implementation of continuous-flow reactors, and promotion of deactivation through addition of LiBr are critical to producing well-defined acrylate polymers with dispersities as low as 1.12. The utility of this approach is established through demonstration of the oxygen-tolerance of the system and application to diverse acrylate monomers, including the synthesis of well-defined di- and triblock copolymers.

中文翻译：

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二甲基二氢吖啶作为光催化剂用于丙烯酸酯单体的有机催化原子转移自由基聚合。

开发具有多种性能的光催化剂（PC）对于有机催化原子转移自由基聚合（O-ATRP）的发展至关重要。二甲基二氢吖啶作为一个新的有机 PC 系列在此亮相，首次能够通过 O-ATRP 对具有挑战性的丙烯酸酯单体进行受控聚合。建立了七种 PC 的结构-性能关系，展示了可调节的光化学和电化学性能，并获得了强氧化性 2 PC.+ 中间体以实现有效的失活。在 O-ATRP 中，PC 的组合、连续流动反应器的实施以及通过添加 LiBr 促进失活对于生产分散度低至 1.12 的明确丙烯酸酯聚合物至关重要。通过演示系统的耐氧性以及对各种丙烯酸酯单体的应用（包括明确的二嵌段和三嵌段共聚物的合成），确立了该方法的实用性。