Cyanines comprising barbiturate group facilitate NIR‐light assisted ATRP under anaerobic and aerobic conditions at two wavelengths using Fe( III ) catalyst

Cyanines with heptamethine pattern namely 5‐(6‐(2‐(3‐ethyl‐1,1‐dimethyl‐1H‐benzo[e]indol‐2(3H)‐ylidene)ethylidene)‐2‐(2‐(3‐ethyl‐1,1‐dimethyl‐1H‐benzo[e]indol‐3‐ium‐2yl) vinyl) cyclo‐hex‐1‐en‐1‐yl)‐1,3‐dimethyl‐2,6‐dioxo‐1,2,3,6‐tetrahydropyrimidin‐4‐olate comprising a barbiturate group facilitate controlled radical polymerization using FeBr 3 in the ppm range applying radiation at 790 nm. Tris(4‐methoylphenyl)phosphine, Tris(2‐pyridylmethyl)amine or tetrabutylammonium bromide served as ligand. The latter showed the best performance resulting in a system needing no amino nitrogen for photo‐ATRP. Ethyl α‐bromophenylacetate worked as initiator. The cyanine interacts with FeBr 3 resulting in a new absorption band at 877 nm that also resulted in formation of polymer exhibiting similar molecular weight but higher dispersity compared to that obtained by 790 nm radiation by exposure with a light‐emitting diode (LED) emitting at 870 nm. This explains the reactivity of the system while other cyanines such as 2‐[2‐[3‐[2‐(1,3‐Dihydro‐1,3,3‐trimethyl‐2H‐indol‐2‐ylidene)‐ethylidene]‐2‐(1‐phenyl‐ 1H‐tetrazol‐5‐ylsulfanyl)‐1‐cyclohexen‐1‐yl]‐ethenyl]‐1,3,3‐trimethyl‐3H‐indolium chloride showed no activity by exposure at 790 nm in combination with FeBr 3 /Br − . Controlled radical polymerization was confirmed by successful chain extension and block copolymerization experiments resulting in polymers, which exhibit a dispersity of about 1.3. Interestingly, the new system comprising the aforementioned barbiturate substituted cyanine, FeBr 3 /Br − and ethyl α‐bromophenylacetate showed a certain oxygen tolerance. Polymers obtained exhibited similar dispersity as those made under inert conditions.