A Well-defined, Versatile Photoinitiator (salen)Co-COCH for Visible Light-initiated Living/controlled Radical Polymerization

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 Jan 9

PMID 29308172

Citations 2

Authors

Yaguang Zhao

Mengmeng Yu

Shuailin Zhang

Zhenqiang Wu

Yuchu Liu

Chi-How Peng

Xuefeng Fu

Affiliations

Soon will be listed here.

Abstract

The control of the polymerization of a wide range of monomers under mild conditions by a single catalyst remains a major challenge in polymer science. We report a versatile, well-defined organocobalt salen complex to control living radical polymerization of different categories of monomers, including acrylates, acrylamides and vinyl acetate, under visible light irradiation at ambient temperature. Both household light and sunlight were effectively applied in the synthesis of polymers with controlled molecular weights and narrow polydispersities. Narrowly dispersed block copolymers (/ < 1.2) were obtained under various conditions. The structures of the polymers were analyzed by H NMR, D NMR, C NMR, GPC, MALDI-TOF-MS and isotopic labeling experiments, which showed that the ω and α ends of the polymer chains were capped with (salen)Co and -COCH segments, respectively, from the photoinitiator (salen)Co-COCH. The ω end was easily functionalized through oxygen insertion followed by hydrolysis from O to -OH. This robust system can proceed without any additives, and offers a versatile and green way to produce well-defined homo and block copolymers.

Citing Articles

One-pot synthesis of hyperbranched polymers via visible light regulated switchable catalysis.

Zhu S, Zhao M, Zhou H, Wen Y, Wang Y, Liao Y Nat Commun. 2023; 14(1):1622.

PMID: 36959264 PMC: 10036521. DOI: 10.1038/s41467-023-37334-x.

Degradable PE-Based Copolymer with Controlled Ester Structure Incorporation by Cobalt-Mediated Radical Copolymerization under Mild Condition.

Zeng T, You W, Chen G, Nie X, Zhang Z, Xia L iScience. 2020; 23(3):100904.

PMID: 32106055 PMC: 7044514. DOI: 10.1016/j.isci.2020.100904.

References

Treat N, Sprafke H, Kramer J, Clark P, Barton B, Read de Alaniz J . Metal-free atom transfer radical polymerization. J Am Chem Soc. 2014; 136(45):16096-101. DOI: 10.1021/ja510389m. View

Peng C, Yang T, Zhao Y, Fu X . Reversible deactivation radical polymerization mediated by cobalt complexes: recent progress and perspectives. Org Biomol Chem. 2014; 12(43):8580-7. DOI: 10.1039/c4ob01427h. View

Lu L, Yang N, Cai Y . Well-controlled reversible addition-fragmentation chain transfer radical polymerisation under ultraviolet radiation at ambient temperature. Chem Commun (Camb). 2005; (42):5287-8. DOI: 10.1039/b512057h. View

Fu C, Xu J, Tao L, Boyer C . Combining Enzymatic Monomer Transformation with Photoinduced Electron Transfer - Reversible Addition-Fragmentation Chain Transfer for the Synthesis of Complex Multiblock Copolymers. ACS Macro Lett. 2022; 3(7):633-638. DOI: 10.1021/mz500245k. View

Treat N, Fors B, Kramer J, Christianson M, Chiu C, Read de Alaniz J . Controlled Radical Polymerization of Acrylates Regulated by Visible Light. ACS Macro Lett. 2022; 3(6):580-584. DOI: 10.1021/mz500242a. View

Fors B, Poelma J, Menyo M, Robb M, Spokoyny D, Kramer J . Fabrication of unique chemical patterns and concentration gradients with visible light. J Am Chem Soc. 2013; 135(38):14106-9. DOI: 10.1021/ja408467b. View

Chavez F, Mascharak P . Co(III)-alkylperoxo complexes: syntheses, structure-reactivity correlations, and use in the oxidation of hydrocarbons. Acc Chem Res. 2000; 33(8):539-45. DOI: 10.1021/ar990089h. View

Liu Y, Ren W, Liu J, Lu X . Asymmetric copolymerization of CO2 with meso-epoxides mediated by dinuclear cobalt(III) complexes: unprecedented enantioselectivity and activity. Angew Chem Int Ed Engl. 2013; 52(44):11594-8. DOI: 10.1002/anie.201305154. View

Magenau A, Strandwitz N, Gennaro A, Matyjaszewski K . Electrochemically mediated atom transfer radical polymerization. Science. 2011; 332(6025):81-4. DOI: 10.1126/science.1202357. View

10.

Ahmed S, Poater A, Childers M, Widger P, LaPointe A, Lobkovsky E . Enantioselective polymerization of epoxides using biaryl-linked bimetallic cobalt catalysts: a mechanistic study. J Am Chem Soc. 2013; 135(50):18901-11. DOI: 10.1021/ja409521z. View

11.

Schaus S, Brandes B, Larrow J, Tokunaga M, Hansen K, Gould A . Highly selective hydrolytic kinetic resolution of terminal epoxides catalyzed by chiral (salen)Co(III) complexes. Practical synthesis of enantioenriched terminal epoxides and 1,2-diols. J Am Chem Soc. 2002; 124(7):1307-15. DOI: 10.1021/ja016737l. View

12.

Jiang X, Wu J, Zhang L, Cheng Z, Zhu X . Highly active ppm level organic copper catalyzed photo-induced ICAR ATRP of methyl methacrylate. Macromol Rapid Commun. 2014; 35(21):1879-85. DOI: 10.1002/marc.201400393. View

13.

Chiang L, Allan L, Alcantara J, Wang M, Storr T, Shaver M . Tuning ligand electronics and peripheral substitution on cobalt salen complexes: structure and polymerisation activity. Dalton Trans. 2013; 43(11):4295-304. DOI: 10.1039/c3dt51846a. View

14.

Goto A, Kwak Y, Fukuda T, Yamago S, Iida K, Nakajima M . Mechanism-based invention of high-speed living radical polymerization using organotellurium compounds and azo-initiators. J Am Chem Soc. 2003; 125(29):8720-1. DOI: 10.1021/ja035464m. View

15.

Ouchi M, Terashima T, Sawamoto M . Transition metal-catalyzed living radical polymerization: toward perfection in catalysis and precision polymer synthesis. Chem Rev. 2009; 109(11):4963-5050. DOI: 10.1021/cr900234b. View

16.

Peretti K, Ajiro H, Cohen C, Lobkovsky E, Coates G . A highly active, isospecific cobalt catalyst for propylene oxide polymerization. J Am Chem Soc. 2005; 127(33):11566-7. DOI: 10.1021/ja053451y. View

17.

Debuigne A, Champouret Y, Jerome R, Poli R, Detrembleur C . Mechanistic insights into the cobalt-mediated radical polymerization (CMRP) of vinyl acetate with cobalt(III) adducts as initiators. Chemistry. 2008; 14(13):4046-59. DOI: 10.1002/chem.200701867. View

18.

Xu J, Jung K, Atme A, Shanmugam S, Boyer C . A robust and versatile photoinduced living polymerization of conjugated and unconjugated monomers and its oxygen tolerance. J Am Chem Soc. 2014; 136(14):5508-19. DOI: 10.1021/ja501745g. View

19.

Yamago S, Ukai Y, Matsumoto A, Nakamura Y . Organotellurium-mediated controlled/living radical polymerization initiated by direct C-Te bond photolysis. J Am Chem Soc. 2009; 131(6):2100-1. DOI: 10.1021/ja8099689. View

20.

Zhao Y, Yu M, Fu X . Photo-cleavage of the cobalt-carbon bond: visible light-induced living radical polymerization mediated by organo-cobalt porphyrins. Chem Commun (Camb). 2013; 49(45):5186-8. DOI: 10.1039/c3cc41466c. View