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Controlling the structure and chemistry of solid electrolyte interphase (SEI) underpins the stability of electrolyte‐electrode interface, and is crucial for advancing rechargeable lithium metal batteries (LMBs). Here, we utilized photo‐controlled copolymerization to achieve the on‐demand synthesis of fluorosulfonyl fluoropolymers as unprecedented artificial SEI layers on Li metal anodes. This work not only enables instant formation of a hybrid polymer‐inorganic interphase that consists of a polymer‐enriched top layer and a LiF‐fortified bottom layer, originating from a single polymeric component, but also imparts various desirable physical properties (e.g. good mechanical strength and flexibility, high ion conductivity, low overpotential) to SEI via a single‐to‐divergent strategy. Model reactions and structural characterizations supported the formation of a divergent fluorinated interphase, which furnished prolonged stabilization of Li deposition, high coulombic efficiency and improved cycling behavior in electrochemical experiments. This work highlights the great potential of exploring reactive polymers as versatile coatings to stabilize Li metal anodes, providing a promising avenue to solve electrode‐electrolyte interfacial problems for LMBs. [ABSTRACT FROM AUTHOR]

Ultrahigh‐molecular‐weight (UHMW) polymers with tailored structures are highly desirable for the outstanding properties. In this work, we developed a novel photoorganocatalyzed controlled radical alternating copolymerizations of fluoroalkyl maleimide and diverse vinyl comonomers, enabling efficient preparation of fluorinated copolymers of predetermined UHMWs and well‐defined structures at high conversions. Versatility of this method was demonstrated by expanding to controlled terpolymerization, which allows facial access toward fluorinated terpolymers of UHMWs and functional pendants. The obtained copolymers exhibited attractive physical properties and furnished thermoplastic, anticorrosive and (super)hydrophobic attributes as coatings on different substrates. Molecular simulations provided insights into the coating morphology, which unveiled a fluorous protective layer on the top surface with polar groups attached to the bottom substrate, resulting in good adhesion and hydrophobicity, simultaneously. This synthetic method and customized copolymers shed light on the design of high‐performance coatings by macromolecular engineering. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Fluorinated polymers are important materials that are widely used in many areas. Herein, we report the development of a metal-free photocontrolled radical polymerization of semifluorinated (meth)acrylates with a new visible-light-absorbing organocatalyst. This method enabled the production of a variety of semifluorinated polymers with narrow molar-weight distributions from semifluorinated trithiocarbonates or perfluoroalkyl iodides. The high performance of 'ON/OFF' control and chain-extension experiments further demonstrate the utility and reliability of this method. Furthermore, to streamline the preparation of semifluorinated polymers, a scalable continuous-flow approach has been developed. Given the broad interest in fluorinated materials and photopolymerization, we expect that this method will facilitate the development of advanced materials with unique properties. [ABSTRACT FROM AUTHOR]

A general, rapid, and efficient method for the copper-catalyzed Finkelstein reaction of (hetero)aromatics has been developed using continuous flow to generate a variety of aryl iodides. The described method can tolerate a broad spectrum of functional groups, including N-H and O-H groups. Additionally, in lieu of isolation, the aryl iodide solutions were used in two distinct multistep continuous-flow processes (amidation and Mg-I exchange/nucleophilic addition) to demonstrate the flexibility of this method. [ABSTRACT FROM AUTHOR]