This review, with over 600 references, summarizes the recent applications of photoredox catalysis for organic transformation and polymer synthesis. Photoredox catalysts are metallo- or organo-compounds capable of absorbing visible light, resulting in an excited state species. This excited state species can donate or accept an electron from other substrates to mediate redox reactions at ambient temperature with high atom efficiency. These catalysts have been successfully implemented for the discovery of novel organic reactions and synthesis of added-value chemicals with an excellent control of selectivity and stereo-regularity. More recently, such catalysts have been implemented by polymer chemists to post-modify polymers in high yields, as well as to effectively catalyze reversible deactivation radical polymerizations and living polymerizations. These catalysts create new approaches for advanced organic transformation and polymer synthesis. The objective of this review is to give an overview of this emerging field to organic and polymer chemists as well as materials scientists.

Photocatalysis in organic and polymer synthesis

Photomediated controlled radical polymerization

Spatial and temporal regulations of ATRP by external stimuli are presented. Various ATRP techniques, eATRP, photoATRP, and mechanoATRP, are controlled by electrical current, light, and mechanical forces, respectively. Conversely, ARGET and SARA ATRP are controlled by chemical reducing agents. ICAR ATRP is a thermally regulated process through decomposition of a radical initiator. The aim of this review is to highlight the use of external regulations in ATRP and to summarize the state-of-the-art and future perspectives, focusing on mechanistic aspects, synthetic procedures, preparation of polymers with complex architectures and functional materials, and their applications.

Externally controlled atom transfer radical polymerization.

Iron-catalyzed atom transfer radical polymerization

Synthetic polymer chemistry endeavors to imitate the spatial and temporal control exhibited within biological systems to obtain well-defined polymeric materials with unique structures, properties, ...

Advances in Polymerizations Modulated by External Stimuli

In this study, photoirradiated Fe-mediated AGET (activators generated by electron transfer) atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was investigated at ambient temperature in N,N-dimethylformamide (DMF) using carbon tetrachloride as initiator, FeCl3·6H2O/bipyridine (Bpy) as catalyst complex, and alcohol as reducing agent. Linear semi-logarithmic plot of conversion vs. time was obtained from the kinetic experiments, and the number-average molecular weight increased linearly with monomer conversion and corresponded to the theoretic values with molecular weight distributions (Mw/Mn) as low as 1.25, which agreed with the character of controlled/living polymerization. The kinds of alcohol played an important role in photoirradiated Fe-mediated AGET ATRP of MMA. The living characteristics were demonstrated through chain extension experiment. The obtained polymer was characterized by proton nuclear magnetic resonance (NMR) and gel permeation chromatography.

Photoirradiated Fe-Mediated AGET ATRP of Methyl Methacrylate in the Presence of Alcohol

A controlled/living photopolymerization of styrene (St) and acrylic acid (AA) mediated by FeCl3·6H2O/tetramethylethylenediamine (TMEDA) was performed in N,N-dimethylformamide using 4-bromomethylbenzophenon (4-BMBP) as photoinitiator at room temperature under UV irradiation. 4-BMBP was first used as ATRP initiator and photoinitiator. A well-defined poly(styrene-co-acrylic acid) with predetermined molecular weight and narrow molecular weight distribution was obtained. The kinetic rule of controlled free radical photopolymerization of St and AA was studied. The kinetic results showed that the obtained random poly(St-co-AA) copolymers produced narrow polydispersity (PDI) within the range of 1.25–1.32 when the conversion was beyond 16.5 %, which was characterized by GPC. The plots of number average molecular weight versus conversion and ln([M]0/[M]) versus time were linear, indicating a controlled/living photopolymerization process. The system proceeded under mild and environmentally friendly conditions. The effects of initiator, catalyst, ligand, and vitamin C(VC) concentrations on polymerization process were investigated. The copolymers were characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H NMR). The methods of Mayo-Lewis (ML), Kelen-Tudos (KT), and Yzrielev-Brokhina Roskin (YBR) were used to calculate the monomer reactivity ratios of controlled/living photopolymerization of St and AA at low conversions under selected conditions. The monomer reactivity ratios of St and AA were calculated to be r
 St = 0.82 and r
 AA = 0.30, respectively in this system. The living characteristics were demonstrated by chain extension experiment.

Photo-induced controlled/living copolymerization of styrene and acrylic acid and determination of reactivity ratios

Abstract In this work, we reported the synthesis of copolymers of poly(styrene-co-acrylonitrile) via single-electron transfer-living radical polymerization using CCl4 as an initiator and Zn(0)/2,2′-bipyridine (Bpy)/FeCl2 as catalyst complexes. The polymerization was carried out at 25°C. The polymerization proceeded in a living fashion based on “nascent” Fe(0) as the source of the transition metal, which was prepared by Zn(0)/FeCl2 in situ. The kinetic experimental results showed that the copolymerization is first-order kinetics. The molecular weights increased linearly with respect to monomer conversion, and narrow polydispersity index values were obtained. The effect of the molar ratio of [Zn(0)]0/[FeCl2]0 on polymerization was investigated. In addition, the polymerization carried out in different solvents was also investigated. The obtained random copolymer was characterized by 1H NMR and gel permeation chromatography. The living characteristic was demonstrated by chain extension experiment.

“Nascent” Fe(0)-mediated living radical copolymerization of styrene and acrylonitrile

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Photoirradiated Fe-Mediated AGET ATRP of Methyl Methacrylate in the Presence of Alcohol

Photo-induced controlled/living copolymerization of styrene and acrylic acid and determination of reactivity ratios

“Nascent” Fe(0)-mediated living radical copolymerization of styrene and acrylonitrile