Photocontrolled Living Polymerization Systems with Reversible Deactivations through Electron and Energy Transfer

• Published in: Macromolecular rapid communications. Vol. 38; no. 13
• Main Authors: Shanmugam, Sivaprakash, Xu, Jiangtao, Boyer, Cyrille
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.07.2017
• Subjects: Addition polymerization; Catalysis; Catalysts; Cationic polymerization; Cells (biology); Chains (polymeric); Chemical synthesis; Cobalt; Deactivation; Decomposition reactions; electron/energy transfer; Electrons; Energy Transfer; Fragmentation; I.R. radiation; Iodine; Light; living polymerization; Metathesis; Near infrared radiation; Photocatalysis; Photocatalysts; Photochemistry - trends; Photoexcitation; Polymer chemistry; Polymerization; Polymers; Polymers - chemistry; spatial/temporal control; visible light; visible light; electron/energy transfer; living polymerization; photocatalysts; spatial/temporal control
• ISSN: 1022-1336; 1521-3927; 1521-3927
• DOI: 10.1002/marc.201700143

Recently, visible‐light‐regulated polymerization has been gaining popularity, as it opens a range of new opportunities for the synthesis of functional polymers and materials. Here, the most recent developments in this field are summarized, which is the use of photocatalysts and catalyst‐free approaches to mediate polymerization upon photoexcitation. These catalysts can transfer an electron or energy to activate an initiator. The recent achievements in light‐regulated atom‐transfer radical polymerization, reversible addition‐fragmentation chain‐transfer polymerization, ring‐opening metathesis polymerization, cobalt‐mediated radical polymerization, iodine‐mediated radical polymerization, and living cationic polymerization are reviewed. Recent development in these fields have solved important challenges in polymer chemistry, such as the development of oxygen‐tolerant polymerization, polymerization mediated by near‐infrared, metal‐free polymerization, and spatial‐, temporal‐, and sequence‐controlled polymerization. Some applications of these techniques will be discussed, such as adapting the current photocatalytic systems to synthesize heterogeneous photocatalysts that act as recyclable photocatalysts and novel light‐mediated approaches for surface functionalization of hybrid materials and living cells. Finally, the existing challenges in polymer chemistry that could be overcome by further development of light‐mediated polymerization techniques are highlighted along with the future directions of this field. Visible‐light‐mediated polymerization has been shaping the progress and direction of the polymer community due to its facile setup and its robust spatial, temporal, and sequence control. The current innovations in visible‐light‐mediated polymerization are highlighted and an overview of the future directions of the field is given.