Ultra‐high‐molecular‐weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible‐deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain‐transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible‐light irradiation. In situ chain‐end extensions from UHMW polymers facilitated the synthesis of well‐defined block copolymers, revealing the excellent chain‐end fidelity achieved by this method.

Per- and polyfluorinated alkyl substances (PFASs) are broadly used as surfactants and water/oil repellents for many decades. However, they are toxic, environmental persistence, and widely detected in water sources. In this work, we developed a fluorous-core nanoparticle-embedded hydrogel (FCH) synthesized by the metal-free tandem photocontrolled radical polymerization under visible-light irradiation. With the FCH material, the scope of absorbable PFASs has been expanded to neutral, anionic, cationic and zwitterionic PFASs with the same adsorbent for the first time. The fluorous nanoparticles exhibited strong and selective affinity toward PFASs without being dramatically influenced by pH levels and background ions, enabling efficient removing of PFASs at high to environmentally relevant concentrations (10 mg/L to 1 μg/L). Furthermore, the FCH network has shown good mechanical performance, facilitating the separation, regeneration, and recycling of adsorbent for multiple runs. These results demonstrate the promise of the FCH material for PFASs separation and adsorbent recycling toward sustainable environment.

Polymerizations of perfluorinated vinyl ethers (PFVEs) providea ni mportant category of fluoropolymers that have received considerable interests in applications.Inthis work, we report the development of an organocatalyzed controlled radical alternating terpolymerization of PFVEs and vinyl ethers (VEs) under visible-light irradiation. This method not only enables the synthesis of ab road scope of fluorinated terpolymers of lowdispersities and high chain-end fidelity,f acilitating tuning the chemical compositions by rationally choosing the type and/or ratio of comonomers,b ut also allows temporal control of chain-growth, as well as the preparation of avariety of novel fluorinated blockcopolymers. To showcase the versatility of this method, fluorinated alternating terpolymers have been synthesized and customized to simultaneously displayav ariety of desirable properties for solid polymer electrolyte design, creating new opportunities in high-performance energy storage devices.

Semifluorinated poly(meth)acrylates are prepared under both organocatalyzed and catalyst-free photo-controlled radical polymerization conditions from simple RAFT agents.

Perfluorinated vinyl ethers (PFVEs) are an important category of monomers for producing fluoropolymers that have found broad applications. In this work, by developing a dibenzo­[a,c]­phenothiazine-based organic photoredox catalyst, we realize photo-controlled radical copolymerization of various PFVEs and unconjugated comonomers (e.g., vinyl esters, vinyl amides, and vinyl ethers) with a high reaction efficiency when exposed to visible-light irradiation, affording a large series of main- and side-chain fluorinated copolymers of low dispersities (D̵ = 1.06–1.24) and good chain-end fidelity at excellent conversions of unconjugated comonomers. Furthermore, this method not only facilitates the “ON/OFF” temporal switch of the chain growth with tunable kinetics for the “ON” states upon altering the wavelengths of light sources but also allows photo-controlled chain extensions with copolymers and homopolymers as additional blocks, presenting a facile and versatile platform to customize complex fluoropolymers for material engineering.

Functional fluoropolymers are important for various applications due to the integrated characteristics of functional groups and fluorocarbon segments. Herein, we developed (1) thermally initiated and visible-light-initiated copolymerization of (trifluoromethyl)­vinyl boronic esters (CF3VBs) and unconjugated alkenes (18 examples, including vinyl ethers, esters, and amides), enabling the efficient synthesis of a broad scope of fluoropolymers in 71–92% yield and variable fractions of gem-CF3/B substituents (F CF3VB = 0.26–0.84) at different molar masses (M n = 5.2–33.4 kDa) and (2) visible-light-initiated cotelomerization of CF3VB and unconjugated alkenes with p-tolyl disulfide as a telogen (M n = 3.6–13.0 kDa). Reactivity ratios for copolymerization were determined by the Meyer–Lowry method at 65 °C (for BVE: r CF3VB = 1.254, r BVE = 0.006; for VAc: r CF3VB = 0.235, r VAc = 0.042; for NVP: r CF3VB = 1.067, r NVP = 0.063). The achieved high fractions of CF3VBs in copolymers are also confirmed by density functional theory (DFT) calculation results. Through post-polymerization modifications, gem-CF3/B units could transform into various copolymers and terpolymers with geminal functionalities (e.g., gem-CF3/OH, gem-CF3/vinyl, gem-CF3/furan). The increase of geminal functionalities enables clearly amplified chemical responsiveness toward pH variation, as demonstrated by fluoropolymers with gem-CF3/OH.

Photo-controlled polymerizations are attractive to tailor macromolecules of complex compositions with spatiotemporal regulation. In this work, with a convenient synthesis for trifluorovinyl boronic ester (TFVB), we report a light-driven organocatalyzed copolymerization of vinyl monomers and TFVB for the first time, which enabled the controlled synthesis of a variety of hybrid fluorine/boron polymers with low dispersities and good chain-end fidelity. The good behaviors of "ON/OFF" switch, chain-extension polymerizations and post-modifications further highlight the versatility and reliability of this copolymerization. Furthermore, we demonstrate that the combination of fluorine and boron could furnish copolymer electrolytes of high lithium-ion transference number (up to 0.83), bringing new opportunities of engineering high-performance materials for energy storage purposes.

Ultra‐high‐molecular‐weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible‐deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain‐transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible‐light irradiation. In situ chain‐end extensions from UHMW polymers facilitated the synthesis of well‐defined block copolymers, revealing the excellent chain‐end fidelity achieved by this method.