Organocatalyzed atom transfer radical polymerization driven by visible light

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Science  27 May 2016:
Vol. 352, Issue 6289, pp. 1082-1086
DOI: 10.1126/science.aaf3935

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Precise control from a metal-free catalyst

Polymerization can be a rather dangerous free for all, with molecules joining randomly in chains at a chaotic pace. One of modern chemistry's great accomplishments has been the development of methods to assemble polymers in steady, orderly steps. However, order comes at a price, and often it's the need for metal catalysts that are hard to remove from the plastic product. Theriot et al. used theory to guide the design of a metal-free light-activated catalyst that offers precise control in atom transfer radical polymerization, alleviating concerns about residual metal contamination (see the Perspective by Shanmugam and Boyer).

Science, this issue p. 1082; see also p. 1053


Atom transfer radical polymerization (ATRP) has become one of the most implemented methods for polymer synthesis, owing to impressive control over polymer composition and associated properties. However, contamination of the polymer by the metal catalyst remains a major limitation. Organic ATRP photoredox catalysts have been sought to address this difficult challenge but have not achieved the precision performance of metal catalysts. Here, we introduce diaryl dihydrophenazines, identified through computationally directed discovery, as a class of strongly reducing photoredox catalysts. These catalysts achieve high initiator efficiencies through activation by visible light to synthesize polymers with tunable molecular weights and low dispersities.

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