Thermally Activated Delayed Fluorescence (TADF) Carbonized Polymer Dots for Efficient Red-Light-Induced Reversible Deactivation Radical Polymerization

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-12-22 DOI:10.1021/acs.macromol.4c02570

Yang Xiao, Wanchao Hu, Bei Liu, Shiyi Li, Changli Lü

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引用次数: 0

Abstract

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.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.