Thermally activated delayed fluorescence (TADF) carbon dots (CDs) have generated interest due to their ability to capture singlet and triplet excitons for efficient emission. However, there are still challenges in achieving high photocatalytic efficiency for traditional TADF CDs prepared by matrix-confinement strategies. Herein, we propose a facile one-pot solvothermal synthesis strategy of matrix-free TADF carbonized polymer dots (CPDs) with an absorption wavelength up to the red-light region and a long delayed fluorescence lifetime of 7.66 μs in DMSO. The unprecedented high-efficiency photocatalytic ability of TADF CPDs as a photocatalyst in both organic and aqueous solvents has been demonstrated for the first time in red-light-triggered photoinduced electron/energy transfer–reversible addition–fragmentation chain transfer (PET-RAFT) polymerization and photoinduced atom transfer radical polymerization (photo-ATRP), with high monomer conversion (>90%) and narrow polymer dispersity (M_w/M_n < 1.20). In addition, the designed CPDs are also successfully utilized in the inverse miniemulsion PET-RAFT polymerization system, expanding the application scope of CDs in photoinduced reversible deactivation radical polymerization (photo-RDRP). This work offers a unique avenue for designing and regulating the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes to achieve matrix-free TADF CD photocatalysts with long-lived excited states for effectively photocatalyzed RDRP.

中文翻译：

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热活化延迟荧光 （TADF） 碳化聚合物点用于高效红光诱导的可逆失活自由基聚合


热激活延迟荧光 （TADF） 碳点 （CD） 因其能够捕获单重态和三重态激子以实现高效发射而引起了人们的兴趣。然而，通过基质限制策略制备的传统 TADF CDs 在实现高光催化效率方面仍然存在挑战。在此，我们提出了一种简单的无基质 TADF 碳化聚合物点 （CPD） 的一锅法溶剂热合成策略，其吸收波长可达红光区域，在 DMSO 中具有 7.66 μs 的长延迟荧光寿命。TADF CPDs作为光催化剂在有机和水性溶剂中前所未有的高效光催化能力，在红光触发的光诱导电子/能量转移-可逆加成-碎裂链转移（PET-RAFT）聚合和光诱导原子转移自由基聚合（光-ATRP）中首次得到证明，具有高单体转化率（>90%）和窄聚合物分散度（M_w/M_n< 1.20）。此外，所设计的 CPD 还成功应用于反相微乳液 PET-RAFT 聚合体系，扩大了 CDs 在光诱导可逆失活自由基聚合 （photo-RDRP） 中的应用范围。这项工作为设计和调节系统间交叉 （ISC） 和反向系统间交叉 （RISC） 过程提供了一种独特的途径，以实现具有长寿命激发态的无基质 TADF CD 光催化剂，以实现有效的光催化 RDRP。