Fluoropolymers have found broad applications for many decades. Considerable efforts have focused on expanding access toward main-chain fluorinated polymers. In contrast to previous polymerizations of gaseous fluoroethylenes conducted at elevated temperatures and with high-pressure metallic vessels, we here report the development of a photoorganocatalyzed reversible-deactivation radical alternating copolymerization of chlorotrifluoroethylene (CTFE) and vinyl ethers (VEs) at room temperature and ambient pressure by exposing to LED light irradiation. This method enables the synthesis of various fluorinated alternating copolymers with low Đ and high chain-end fidelity, allowing an iterative switch of the copolymerization between “ON” and “OFF” states, the preparation of fluorinated block alternating copolymers, as well as postsynthetic modifications.

Continuous-flow chemistry represents a robust setting for photochemical reactions. We have developed the first computer-aided droplet-flow platform for photocontrolled radical polymerization. This method allows precise and scalable living polymerizations of monomers at high concentrations in flow, even when solids are generated. The consistent good performance of polymerization during the programmed change of reaction conditions demonstrates the reliability and utility of this method. Furthermore, the droplet-flow approach not only streamlines an automated high-throughput living polymerization (275 droplets of samples in 11 min), which enables the rapid generation of copolymer libraries for low-cost structure–property relationship screening, but also allows on-line switching to desirable reaction conditions for the scale-up (co)­polymerization purpose.

Aromatic sulfonyl halides are readily accessible from many sources. With newly synthesized N-arylphenothiazine catalysts, organocatalyzed photoredox polymerization has been developed with arylsulfonyl halides initiators using white or purple LEDs light sources. This method allows the preparation of poly(meth)acrylates and poly(meth)acrylamides possessing a broad scope of (hetero)aryl chain ends without metal-contamination concern. Investigations such as MALDI-TOF analysis, chain extension, and "ON/ OFF" control experiments confirmed the fidelity of the polymer structure and reliability of this method. Moreover, this method facilitates the two-step preparation of brush polymers from polystyrene through an electrophilic aromatic substitution/ organocatalyzed photopolymerization sequence.

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A new method to construct 4-hydroxyalkyl-quinoline derivatives is described via Cu(i) and Au(i) sequential catalyzed cyclization of anilines with aldehyde derivatives and aliphatic alkynes, respectively.