Exploiting Metalloporphyrins for Selective Living Radical Polymerization Tunable over Visible Wavelengths

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• 作者：Sivaprakash Shanmugam ; Jiangtao Xu ; Cyrille Boyer
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：July 22, 2015
• 年：2015
• 卷：137
• 期：28
• 页码：9174-9185
• 全文大小：795K
• ISSN：1520-5126

文摘

The use of metalloporphyrins has been gaining popularity particularly in the area of medicine concerning sensitizers for the treatment of cancer and dermatological diseases through photodynamic therapy (PDT), and advanced materials for engineering molecular antenna for harvesting solar energy. In line with the myriad functions of metalloporphyrins, we investigated their capability for photoinduced living polymerization under visible light irradiation over a broad range of wavelengths. We discovered that zinc porphyrins (i.e., zinc tetraphenylporphine (ZnTPP)) were able to selectively activate photoinduced electron transfer鈥搑eversible addition鈥揻ragmentation chain transfer (PET-RAFT) polymerization of trithiocarbonate compounds for the polymerization of styrene, (meth)acrylates and (meth)acrylamides under a broad range of wavelengths (from 435 to 655 nm). Interestingly, other thiocarbonylthio compounds (dithiobenzoate, dithiocarbamate and xanthate) were not effectively activated in the presence of ZnTPP. This selectivity was likely attributed to a specific interaction between ZnTPP and trithiocarbonates, suggesting novel recognition at the molecular level. This interaction between the photoredox catalyst and trithiocarbonate group confers specific properties to this polymerization, such as oxygen tolerance, enabling living radical polymerization in the presence of air and also ability to manipulate the polymerization rates (k_p^app from 1.2鈥?.6 脳 10^鈥? min^鈥?) by varying the visible wavelengths.