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      RAFT-mediated, visible light-initiated single unit monomer insertion and its application in the synthesis of sequence-defined polymers

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          In this communication, we report a catalyst-free methodology for single unit monomer insertion (SUMI) into reversible addition–fragmentation chain transfer (RAFT) agents initiated by low intensity visible light.


          In this communication, we report a catalyst-free methodology for single unit monomer insertion (SUMI) into reversible addition–fragmentation chain transfer (RAFT) agents initiated by low intensity visible light. This method is applicable to broad range of monomer families (monosubstituted vinyl monomers) and allows for the preparation of the corresponding single monomer insertion product in high yields (typically >90%; isolated yields after chromatography 60–80%). The fidelity of the end-functional SUMI products is demonstrated with use of the SUMI products in RAFT polymerization and by using the tools of conventional chemistry (thiol–ene and esterification reactions). A uniform oligomer comprising five discrete vinyl monomer repeat units was synthesized by an iterative strategy comprising three consecutive SUMI reactions and two intermediate esterification and thiol–ene steps. We thus demonstrate a new protocol for incorporating the rich functionality of available vinyl monomers into polymers where sequence is precisely defined at the monomer level.

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          Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis.

          The merits of thiol-click chemistry and its potential for making new forays into chemical synthesis and materials applications are described. Since thiols react to high yields under benign conditions with a vast range of chemical species, their utility extends to a large number of applications in the chemical, biological, physical, materials and engineering fields. This critical review provides insight into emerging venues for application as well as new mechanistic understanding of this exceptional chemistry in its many forms (81 references).
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            A robust and versatile photoinduced living polymerization of conjugated and unconjugated monomers and its oxygen tolerance.

            Controlled/living radical polymerization techniques have transformed polymer chemistry in the last few decades, affording the production of polymers with precise control over both molecular weights and architectures. It is now possible to synthesize almost an infinite variety of macromolecules using nonspecialized equipment, finding applications in high-tech industry. However, they have several shortcomings. Until recently, living radical polymerizations could not be controlled by an external stimulus, such as visible light, pH, mechanical, chemical, etc. Moreover, they are usually sensitive to trace amounts of oxygen in the system. In this Article, we report a photoinduced living polymerization technique, which is able to polymerize a large range of monomers, including conjugated and unconjugated monomers, using ultralow concentrations of an iridium-based photoredox catalyst (typically 1 ppm to monomers) and a low energy visible LED as the light source (1-4.8 W, λ(max) = 435 nm). The synthesis of homopolymers with molecular weights ranging from 1000 to 2,000,000 g/mol was successfully achieved with narrow molecular weight distributions (M(w)/M(n) < 1.3). In addition, chain extensions of poly(methacrylate)s, poly(styrene), poly(N-vinyl pyrrolidinone), poly(vinyl ester)s, and poly(acrylate)s were performed to prepare diblock copolymers. The reusability of the catalyst was demonstrated by the synthesis of a decablock polymer by multiple chain extensions. Most importantly, this process was employed to prepare well-defined polymers and multiblock copolymers in the presence of air.
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              From precision polymers to complex materials and systems


                Author and article information

                Polymer Chemistry
                Polym. Chem.
                Royal Society of Chemistry (RSC)
                : 8
                : 32
                : 4637-4643
                [1 ]Centre for Advanced Macromolecular Design (CAMD) and Australian Centre for NanoMedicine (ACN)
                [2 ]School of Chemical Engineering
                [3 ]UNSW Australia
                [4 ]Sydney
                [5 ]Australia
                [6 ]Materials Research Laboratory and Departments of Materials
                [7 ]Chemistry and Biochemistry
                [8 ]University of California
                [9 ]Santa Barbara
                [10 ]USA
                [11 ]CSIRO Manufacturing
                [12 ]Clayton
                © 2017


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