Supporting Information

Transcription

1 Supporting Information A Robust and Versatile Photoinduced Living Polymerization of Conjugated and Unconjugated Monomers and Its Oxygen Tolerance Jiangtao Xu a,b Kenward Jung, a Amir Atme, b Sivaprakash Shanmugam, a and Cyrille Boyer a,b * a- Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering, UNSW Australia, Sydney, NSW 2052, Australia b- Australian Centre for NanoMedicine, School of Chemical Engineering, UNSW Australia, Sydney, NSW 2052, Australia cboyer@unsw.edu.au Experimental Section Materials: Methyl methacrylate (MMA, 99%), tert-butyl methacrylate (tbuma, 99%), tert-butyl acrylate (tbua, 99%), n-butyl acrylate (nbua, 99%), methyl acrylate (MA, 99%), styrene (99%), vinyl acetate (VAc, 99%), oligo (ethylene glycol) methyl ether methacrylate (OEGMA, average M n 300), oligo(ethylene glycol) methyl ether acrylate (OEGA, average M n 480), N,N-dimethylacrylamide (DMA, 99%), N-isopropylacrylamide (NIPAAm, 97%), N-vinyl pyrrolidinone (NVP, 97%), vinyl pivalate (VP, 99%) dimethyl vinylphosphonate (DVP, 95%), isoprene (99%), tetrabutylammonium tetrafluoroborate (+99%) and tris[2-phenylpyridinato- C 2,N]iridium(III) (fac-[ir(ppy) 3 ], 99%) were all purchased from Aldrich. The monomers were de-inhibited by percolating over a column of basic alumina (Ajax Chemical, AR). N-(2-hydroxypropyl) methacrylamide (HPMA, Polysciences Inc., 97%) was used as received. N,N-dimethylformamide (DMF, 99.8%, Ajax Chemical), dimethyl sulfoxide (DMSO, Ajax Chemical), n-hexane (Ajax Chemical), methanol (Ajax S1

2 Chemical), diethyl ether (Ajax Chemical), and petroleum spirit (Ajax Chemical) were also used as received. Thiocarbonylthiol compounds: 4-cyanopentanoic acid dithiobenzoate (CPADB), 2-(n-butyltrithiocarbonate)- propionic acid (BTPA), and methyl 2-[(ethoxycarbonothioyl)sulfanyl]propanoate (xanthate) were synthesized according to literature procedures. Instrumentation Gel permeation chromatography (GPC) was performed using tetrahydrofuran (THF) or dimethylacetamide (DMAc) as the eluent. The GPC system was a Shimadzu modular system comprising an auto injector, a Phenomenex 5.0 µm beadsize guard column ( mm) followed by four Phenomenex 5.0 µm bead-size columns (10 5, 10 4, 10 3 and 10 2 Å) for DMAc system, two MIX C columns provided by Polymer Lab for THF system, and a differential refractive-index detector and a UV detector. The system was calibrated with narrow molecular weight distribution polystyrene standards with molecular weights of 200 to 10 6 g mol -1. UV-vis Spectroscopy. UV-vis spectra were recorded using a CARY 300 spectrophotometer (Varian) equipped with a temperature controller. Nuclear magnetic resonance (NMR) spectroscopy was carried out on a Bruker DPX 300 spectrometer operating at 400 MHz for 1 H and 100 MHz for 13 C using CDCl 3 and DMSO-d 6 as solvents and tetramethylsilane (TMS) as a reference. Data was reported as follows: chemical shift (δ) measured in ppm downfield from TMS. Fluorescence spectroscopy. Fluorescence spectra were recorded using Agilent fluorescent spectrometer. Cyclic voltammetry. Electrochemical measurements were carried out on a PAR model 173 potentiostat, equipped with a PAR 175 universal programmer on a computer-controlled Autolab PGSTAT30 potentiostat run by a PC with GPES software. All experiments were performed in a three-electrode cell system under argon atmosphere. Photopolymerization reactions were carried out under visible light irradiation by a 1 m blue LED strip (λ max = 435 nm, 4.8 Watts) surrounding the reaction vessels (SI, Figure S1). S2

3 General procedures for kinetic studies of photoinduced living polymerization. In a typical experiment of kinetic study of MMA polymerization, a 5 ml glass vial was equipped with a rubber septum and charged with DMSO (2 ml), MMA (1.72 g, 17.2 mmol), CPADB (24 mg, mmol), and Ir(ppy) 3 (0.011 mg, mmol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts, λ max = 435 nm) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (DMAc) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). For the kinetic study of MA polymerization, a 5 ml glass vial was equipped with a rubber septum and charged with DMSO (2 ml), MA (1.74 g, 20.2 mmol), BTPA (24 mg, mmol), and Ir(ppy) 3 (0.013 mg, mmol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by blue a LED strip (4.8 Watts, λ max = 435 nm) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (DMAc) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). For the kinetic study of styrene polymerization, a 5 ml glass vial was equipped with a rubber septum and charged with DMSO (2 ml), St (2.11 g, 21.1 mmol), BTPA (24 mg, mmol), and Ir(ppy) 3 (0.132 mg, mmol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts, λ max = 435 nm) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (DMAc) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). For the kinetic study of vinyl acetate (VAc) polymerization, a 5 ml glass vial was equipped with a rubber septum and charged VAc (1.72 g, 20 mmol), xanthate (23.8 mg, 0.10 mmol), and Ir(ppy) 3 (0.065 mg, mol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then S3

4 irradiated by a blue LED strip (4.8 Watts, λ max = 435 nm) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (DMAc) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). Typical polymerization of N-vinyl pyrrolidinone (NVP), a 5 ml glass vial was equipped with a rubber septum and charged NVP (2.22 g, 20 mmol), MADIX (28.1 mg, mmol), and Ir(ppy) 3 (0.130 mg, mol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts, λ max = 435 nm) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (DMAc) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). Typical polymerization of vinyl pivalate (VP), a 5 ml glass vial was equipped with a rubber septum and charged VP (2.56 g, 20 mmol), MADIX (23.8 mg, 0.10 mmol), and Ir(ppy) 3 (0.130 mg, mol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts, λ max = 435 nm) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (THF) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). Typical polymerization of dimethyl vinylphosphonate (DVP), a 5 ml glass vial was equipped with a rubber septum and charged DVP (2.72 g, 20 mmol), MADIX (23.8 mg, 0.20 mmol), and Ir(ppy) 3 (0.130 mg, mol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts, λ max = 435 nm) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (DMAc) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). S4

5 General procedure for the preparation of diblock copolymers by photoinduced livingpolymerization. In a typical experiment synthesizing the diblock copolymer poly(methyl methacrylate)-b-poly(tert-butyl methacrylate) (PMMA-b-PtBMA), a 5 ml glass vial was equipped with a rubber septum and charged with DMSO (0.5 ml), MMA (0.43 g, 4.3 mmol), CPADB (6 mg, mmol), Ir(ppy) 3 ( mg, mmol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts) as light source at room temperature for 24 h. The final solution was precipitated in mixture of methanol/petroleum spirit (1/1, v/v) with stirring. The pink precipitate was collected, re-dissolved in a minimal amount of dichloromethane, and precipitated a second time from the mixture of methanol/petroleum spirit (1/1, v/v). The pink precipitate was then collected and dried to give desired products: M n = , M n /M w = For the chain extension, a 5 ml glass vial was equipped with a rubber septum and charged with DMSO (0.5 ml), MMA (0.29 g, 2.9 mmol), PMMA macro-initiator (0.2 g, M n = g/mol, mmol), and Ir(ppy) 3 ( mg, mmol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts) at room temperature for 24h. The final solution was precipitated in methanol with stirring. The pink precipitate was collected, re-dissolved in a minimal amount of dichloromethane, and precipitated a second time from methanol. The pink precipitate was then collected and dried to give desired products: M n = g/mol, M n /M w = For the chain extension using PNVP as macro-initiator, a 5 ml glass vial was equipped with a rubber septum and charged with DMSO (0.5 ml), VAc (0.25 g, 2.9 mmol), PNVP macro-initiator (0.05 g, M n = 6900 g/mol, mmol), and Ir(ppy) 3 ( mg, mmol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts, λ max = 435 nm) at room temperature for 24h. The final solution was precipitated in diethyl ether. The precipitate was collected. The block copolymer was analyzed by GPC. S5

6 Preparation of decablock copolymer of MA by photoinduced living polymerization without purification. Methyl acrylate (MA, 0.3 g, 3.49 mmol), DMSO (0.4 ml), BTPA (6.9 mg, mmol), and Ir(ppy) 3 ( mg, mmol) were charged to a pear-shaped flask fitted with a rubber septum, and the mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts) at room temperature. After 4h, an aliquot of the reaction mixture was withdrawn for 1 H NMR and GPC (THF) analysis. The sample for 1 H NMR was simply diluted with CDCl 3 and the sample for GPC (THF) analysis was diluted with THF and filtered through a Teflon filter (0.45µm pore size). For the iterative chain extensions, a further 0.3 g of a degassed monomer (in 50 v-% DMSO for 2-4 blocks, and 25 v-% DMSO for 5-10 blocks) solution was added via a nitrogen-purged syringe, and again the solution was allowed to polymerize at RT for 4h. The above polymerization-sampling-extension procedure was repeated as required. General procedures for kinetic studies of photoinduced living polymerization under air. In a typical experiment of kinetic study of MMA polymerization, a 4 ml glass vial was equipped with a rubber septum and charged with DMSO (1.5 ml), MMA (1.5 ml, 1.45 g, 14.5 mmol), CPADB (19.5 mg, mmol), and Ir(ppy) 3 (0.009 mg, mmol). Without nitrogen pruging, the mixture was irradiated by a blue LED strip (4.8 Watts) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined interval times and analyzed by 1 H NMR (CDCl 3 ) and GPC (THF) to measure the conversions, number average molecular weights (M n ), and polydispersities (M n /M w ). Compatibility test of chain transfer agent, CPADB, and photocatalyst, Ir(ppy) 3. A 5 ml glass vial was equipped with a rubber septum and charged with DMSO-d 6 (2.0 ml), CPADB (24 mg, mmol), and Ir(ppy) 3 (0.562 mg, mmol). The mixture was covered in aluminum foil and degassed by N 2 for 20 min. The mixture was then irradiated by a blue LED strip (4.8 Watts) at room temperature. Aliquots were withdrawn by nitrogen-purged syringes from the reaction mixture at predetermined intervals and analyzed by 1 H NMR spectroscopy (DMSO-d 6 ). S6

7 Additional Schemes: Scheme S1. Chemical Structure of photoredox catalyst fac-[ir(ppy)] (ppy = 2-pyridylphenyl). S7

8 Scheme S2. Chemical structures of monomers and thiocarbonylthio compounds (chain transfer agents, CTAs): (a) methyl methacrylate (MMA), (b) methyl acrylate (MA), (c) vinyl acetate, (d) styrene (St), (e) N,Ndimethylacrylamide (DMA), (f) N-(2-hydroxypropyl) methacrylamide (HPMA), (g) oligoethylene glycol methyl ether methacrylate (OEGMA), (h) dimethyl vinylphosphonate (DVP), (i) vinyl pivalate (VP), (j) N-vinyl pyrolidinone (NVP), (k) tert-butyl acrylate (tbua), (l) N-isopropylacrylamide (NIPAAm), (m) oligoethylene glycol methyl ether acrylate (OEGMA), (n) isoprene; 4-cyanopentanoic acid dithiobenzoate (CPADB), 2-(nbutyltrithiocarbonate)-propionic acid (BTPA) and methyl 2-[(ethoxycarbonothioyl)sulfanyl]propanoate (xanthate). S8

9 initiator. Scheme S3. Synthesis of diblock copolymer via photoinduced living polymerization using PMMA macro- S9

10 Additional Figures: Figure S1. Experimental Setup for photopolymerization using 4.8 W blue LED light. S10

11 Part 1. Investigation of photoinduced living polymerization mechanism using fluorescence spectroscopy and cyclic voltammetry. Figure S2. Cyclic voltammogram of BTPA in acetonitrile to determine redox potential. Note: the analysis was performed using tetrabutylammonium tetrafluoroborate (0.1M) as electrolyte in acetonitrile ([BTPA] = 10-3 M), using a platinum (Pt) electrode (potential determined versus Ag/AgCl electrode used as electrode of reference and then converted to saturated calomel electrode) at 25 o C. Figure S3. Excitation and emission spectra of photoredox catalyst fac-[ir(ppy) 3 ] in DMSO. λ max, ex = 376 nm, λ max, em = 524 nm. S11

12 Part 2. Polymerization of methyl methacrylate by photoinduced living polymerization Synthesis of different molecular weights of PMMA using photoinduced living polymerization. Table S1. Examples of PMMA synthesized by photoinduced living polymerization using DMSO as solvent, CPADB and 4.8W blue LED lamp as light source. Entry Experimental Conditions a [M]:[CPADB]:[Ir] [Ir]/[M] Conv. b (%) M n, th. c (g/mol) M n, GPC d (g/mol) M w /M n SMMA1 100:1: ppm SMMA2 100:1: ppm (7 180) e 1.09 SMMA3 200:1: ppm SMMA4 800: 1: ppm Note: a) The reactions were performed in DMSO at room temperature for 24h; b) Monomer conversion determined by 1 H NMR spectroscopy was calculated by the following equation: α = (1 - [(I ppm /2)/(I 3.5ppm /3)]) 100; c) Theoretical molecular weight calculated using the following equation: M n, th. = [MMA] 0 /[CPADB] 0 MW MMA α + MW CPADB, where [MMA] 0, [CPADB] 0, MW MMA, α and MW CPADB correspond to MMA and CPADB concentration, molar mass of MMA, monomer conversion and molar mass of CPADB; d) Molecular weight and polydispersity determined by GPC analysis (DMAc used as eluent); e) Molecular weight determined by NMR analysis using M n, NMR = (I 3.5ppm /3)/(I ppm /5) MW MMA + MW CPADB, where I 3.5ppm and I ppm correspond to integrals of signal at 3.5 ppm and ppm attributed to OCH 3 of MMA and phenyl group of CPADB agent, respectively. S12

13 Table S2. Preliminary results of PMMA polymers synthesized by photoinduced living polymerization in other solvents. [Ir]/[M] Conv. b Entry Solvent (%) c d M n, th. M n, GPC (g/mol) (g/mol) M w /M n SMMA5 Acetontrile 50 ppm SMMA6 Toluene 50 ppm SMMA7 Methanol 50 ppm Note: a) The reactions were performed at room temperature for 6 h using 4.8 W blue LED lamp as light source; molar ratio [MMA]:[CPADB]:[ fac-[ir(ppy) 3 ]] = 200:1: ; b) Monomer conversion determined by 1 H NMR spectroscopy was calculated by the following equation: α = (1 - [(I ppm /2)/(I 3.5ppm /3)]) 100; c) Theoretical molecular weight calculated using the following equation: M n, th. = [MMA] 0 /[CPADB] 0 MW MMA α + MW CPADB, where [MMA] 0, [CPADB] 0, MW MMA, α and MW CPADB correspond to MMA and CPADB concentration, molar mass of MMA, monomer conversion and molar mass of CPADB; d) Molecular weight and polydispersity determined by GPC analysis (DMAc used as eluent). S13

14 Kinetic study of polymerization of MMA using photoinduced living polymerization technique (a) (b) S14

15 (c) Figure S4. Photoinduced living polymerization of MMA at the photocatalyst ratio ([catalyst]/[mma]) of 2 ppm in DMSO. a) ( ) M n vs. conversion and ( ) M w /M n vs. conversion; b) ln([m] 0 /[M] t ) vs. exposure time, with [M] 0 and [M] t correspond to the concentrations of monomers at time zero and t, respectively; c) GPC curves at different times. Note: The reactions were performed in DMSO at room temperature using CPADB as chain transfer agent and 4.8W blue LED light, molar ratio [MMA]:[CPADB] equal to 200 :1. S15

16 End-group characterization of PMMA synthesized by photoinduced living polymerization. Figure S5. 1 H NMR spectrum of purified PMMA polymer synthesized by photoinduced living polymerization for 24h using the CPADB and 4.8 W blue LED lamp as light source (M n, NMR = 7180 g/mol, M n, GPC = 7320 g/mol, monomer conversion 73%, Table S1, entry SMMA2). Note: a) Reaction condition: molar ratio [MMA]:[CPADB]:[ fac-[ir(ppy) 3 ]] = 200:1: in DMSO at room temperature; b) Theoretical molecular weight calculated using the following equation: M n, th. = [MMA] 0 /[CPADB] 0 MW MMA α + MW CPADB, where [MMA] 0, [CPADB] 0, MW MMA, α and MW CPADB correspond to MMA and CPADB concentration, molar mass of MMA, monomer conversion and molar mass of CPADB; c) Molecular weight and polydispersity determined by GPC analysis (DMAc used as eluent); e) Molecular weight determined by NMR analysis using M n, NMR = (I 3.5ppm /3)/(I ppm /5) MW MMA + MW CPADB, where I 3.5ppm and I ppm correspond to integrals of signal at 3.5 ppm and ppm attributed to OCH 3 of MMA and phenyl group of CPADB, respectively. S16

17 Absorbance (a.u.) Wavelength (nm) Figure S6. UV-vis spectrum of purified PMMA polymer synthesized by photoinduced living polymerization using CPADB and 4.8 W blue LED lamp as light source in DMSO for 24 h (M n, NMR = 7180 g/mol, M n, GPC = 7320 g/mol, Table S1, entry SMMA2). Note 1: The signal at 305 nm is attributed to C=S bond of dithioester. Note 2: The dithiocarbonate end group functionality was determined to be ~100% using the following equation: F end group = (Abs/ε CPADB )/[PMMA], where Abs, ε CPADB and [PMMA] correspond to absorbance, extension coefficient of CPADB agent 1 and PMMA concentration, respectively. PMMA concentration was calculated using the molecular weight determined by GPC. S17

18 RI response (a.u.) UV response (a.u.) Log(M) Figure S7. Comparison of molecular weight distributions recorded using a RI and UV (λ = 305 nm) detector for purified PMMA prepared by photoinduced living polymerization. M n, NMR = 7180 g/mol, M n, GPC = 7320 g/mol, Table S1, entry SMMA2. This result confirmed that all polymer chains were functionalized by a dithioester end group. S18

19 Control experiment for compatibility test. Figure S8. 1 H NMR spectra of CBADB in DMSO with fac-[ir(ppy) 3 ] before and after 24h exposure under 4.8 W blue LED light. S19

20 Chain extensions using PMMA macro-initiators prepared by photoinduced living polymerization. PMMA macroinitiator, M n = 13800, PDI = 1.08 PMMA-b-PMMA, M n = 24710, PDI = Retention Time (min) Figure S9. GPC traces of PMMA macro-initiator and PMMA-b-PMMA block copolymers synthesized by photoinduced living polymerization. (See Table S4 for experimental conditions). PMMA macroinitiator, M n =7100, PDI=1.08 PMMA-b-POEGMA, M n =15330, PDI= Retention Time (min) Figure S10. GPC traces of PMMA macro-initiator and PMMA-b-POEGMA block copolymers synthesized by photoinduced living polymerization. (See Table S4 for experimental conditions). S20

21 PMMA macroinitiator, M n = 13880, PDI = 1.08 PMMA-b-PtBMA, M n = 23390, PDI = Retention Time (min) Figure S11. GPC traces of PMMA macro-initiator and PMMA-b-PtBuMA block copolymers synthesized by photoinduced living polymerization. (See Table S4 for experimental conditions). Table S3. Molecular weights and polysidersities (M w /M n ) of block copolymers synthesized by photoinduced living polymerization using PMMA macro-initiators. Conversion a Copolymers (%) b c M n, Th.. M n, GPC (g/mol) (g/mol) M w /M n PMMA macro-initiator PMMA-b-PMMA PMMA-b-PtBuMA PMMA macro-initiator PMMA-b-POEGMA Note: The reactions were performed in DMSO at room temperature using 4.8 W blue LED lamp as light source and molar ratio [catalyst]/[monomer] = 1ppm; a) Monomer conversion determined by 1 H NMR spectroscopy; b) Theoretical molecular weight calculated using the following equation: M n, th. = [monomer] 0 /[PMMA-macro] 0 MW monomer α + MW PMMA-macro, where [monomer] 0, [PMMA-macro] 0, MW MMA, α and MW PMMA-macro correspond to MMA and PMMA macro-initiator concentration, molar mass of MMA, monomer conversion and molar mass of PMMA macro-initiator; d) molecular weight and polydispersity determined by GPC analysis (DMAc used as eluent). S21

22 1.0 RI response Log M (g/mol) Figure S12. Molecular weight distributions of PMMA macro-initiator, PMMA-b-PMMA and PMMA-b- PMMA-b-PMMA block copolymers synthesized by photoinduced living polymerization (PMMA-macroinitiator: M n, GPC = g/mol, M w /M n = 1.09, MMA conversion 99+%; PMMA-b-PMMA: M n, GPC = g/mol, M w /M n = 1.14, MMA conversion 98%; M n, GPC = g/mol, M w /M n = 1.30, MMA conversion 75%). S22

23 Part 3: Polymerization of other conventional conjugated monomers, including acrylate, (meth)acrylamide, styrene and isoprene by photoinduced living polymerization 1 H NMR spectrum of PHPMA polymers prepared by photoinduced living polymerization. Figure S13. 1 H NMR spectrum of purified PHPMA polymer synthesized by photoinduced living polymerization using CPADB and 4.8 W blue LED lamp as light source in DMSO during 24h (M n, NMR = g/mol, M n, GPC = g/mol, HPMA conversion 21%, Table 2, # 3) Note: a) The reaction was performed using a molar ratio [HPMA]:[CPADB]:[ fac-[ir(ppy) 3 ]] = 200:1: in DMSO at room temperature and a 4.8 W Blue LED lamp as light source; b) Monomer conversion determined by 1 H NMR spectroscopy was calculated by the following equation: α = (1 - [(I 5.5ppm )/(I ppm )]) 100; c) Molecular weight and polydispersity determined by GPC analysis (DMAc used as eluent); d) molecular weight determined by NMR analysis using M n, NMR = (I 3.8ppm /1)/(I 7.8pm /2) MW HPMA + MW CPADB, where I 3.8ppm and I 7.8ppm correspond to integrals of signal at 3.8ppm and 7.8ppm attributed to CH of HPMA and phenyl group of CPADB agent (Z-group). S23

24 Synthesis of different molecular weights of PMA polymers using photoinduced living polymerization. Table S4. Examples of PMA synthesized by photoinduced living polymerization using BTPA and 4.8 W blue LED lamp as light source. Entry Experimental Conditions a [M]:[BTPA]:[Ir] Conv. b (%) M n, theoretical c (g/mol) M n, GPC d (g/mol) M w /M n SMA1 20:1: SMA2 100:1: (8 500) e 1.08 SMA :1: Note: a) The reactions were performed in DMSO at room temperature for 3 h; b) Monomer conversion determined by 1 H NMR spectroscopy was calculated by the following equation: α = (1 - [(I ppm /3)/(I 3.6ppm /3)]) 100; c) Theoretical molecular weight calculated using the following equation: M n, theo = [MA] 0 /[BTPA] 0 MW MA α + MW BTPA, where [MA] 0, [BTPA] 0, MW MA, α and MW BTPA correspond to MA and BTPA concentration, molar mass of MA, monomer conversion and molar mass of BTPA; d) Molecular weight and polydispersity (M w /M n ) determined by GPC analysis (THF used as eluent). The molecular weights were recalculated using Mark-Houwing coefficients of PST in THF (K = dl/g and α = 0.716) and PMA in THF (K = dl/g and α = 0.660); 2,3 e) molecular weight determined by NMR analysis using M n, NMR = (I 3.6ppm /I 0.8ppm ) MW MA + MW BTPA, where I 3.6ppm and I 0.8ppm correspond to integrals of signal at 3.6 ppm and 0.8ppm attributed to OCH 3 of MA and methyl group (Z-group) of BTPA agent and using M n, NMR = (I 3.5ppm /I 1.3ppm ) MW MA + MW BTPA, where I 3.6ppm and I 0.8ppm correspond to integrals of signal at 3.6ppm and 1.3ppm attributed to OCH 3 of MA and methyl group (R-group) of BTPA agent. S24

25 Kinetic study of MA using photoinduced living polymerization. (a) (b) S25

26 (c) Figure S14. GPC traces of MA synthesized by photoinduced living ppolymerization at the photocatalyst ratio ([catalyst]/[ma]) of 1 ppm in DMSO at different reaction times, THF employed as eluent. Note: The reaction was performed using a molar ratio of [MA]:[BTPA]:[ fac-[ir(ppy) 3 ]] = 200:1: in DMSO at room temperature and a 4.8 W blue LED lamp as light source. S26

27 End group characterization of PMA. Figure S15. 1 H NMR spectrum of purified PMA polymer synthesized by photoinduced living polymerization using BTPA and 4.8 W blue LED lamp as light source (M n, NMR = g/mol, M n, GPC = g/mol, monomer conversion >98%, Table S4, entry SMA2). Note: a) The reaction was performed using a molar ratio [MA]:[BTPA]:[ fac-[ir(ppy) 3 ]] = 100:1: in DMSO at room temperature and a 4.8 W Blue LED lamp as light source; b) Monomer conversion determined by 1 H NMR spectroscopy was calculated by the following equation: α = (1 - [(I 5.5ppm )/(I 3.6ppm /3)]) 100; c) Theoretical molecular weight calculated using the following equation: M n, theo = [MA] 0 /[BTPA] 0 MW MA α + MW BTPA, where [MA] 0, [BTPA] 0, MW MA, α and MW BTPA correspond to MA and BTPA concentration, molar mass of MA, monomer conversion and molar mass of BTPA; d) molecular weight and polydispersity determined by GPC analysis (THF used as eluent); e) molecular weight determined by NMR analysis using M n, NMR = (I 3.6ppm /3)/(I 0.8ppm /5) MW MA + MW BTPA, where I 3.6ppm and I 0.8ppm correspond to integrals of signal at 3.5 ppm and 0.8ppm attributed to OCH 3 of MA and methyl group of BTPA. S27

28 Absorbance (a.u.) Wavelength (nm) Figure S16. UV-vis spectrum of purified PMA polymer synthesized by photoinduced living polymerization using BTPA and 4.8 W blue LED lamp as light source in DMSO for 3h (M n, NMR = g/mol, M n, GPC = g/mol, monomer conversion >98%, Table S4, entry SMA2). S28

29 UV response (a.u.) RI response (a.u.) Log(M) Figure S17. Comparison of molecular weight distributions recorded using a RI and UV (λ = 305 nm) detector for purified PMA prepared by photoinduced living polymerization using BTPA and 4.8 W blue LED lamp as light source in DMSO for 3h (M n, NMR = g/mol, M n, GPC = g/mol, monomer conversion >98%, Table S4, entry SMA2). This result confirms that the polymer chains were functionalized by a trithiocarbonate end group. S29

30 Kinetic study of St using photoinduced living polymerization. (a) (b) S30

31 (c) Figure S18. Photoinduced living polymerization of styrene using [fac-[ir(ppy) 3 ]]/[styrene] molar ratio of 10 ppm in DMSO and 4.8 W Blue LED lamp as light source. a) M n, GPC ( ) and M w /M n ( ) vs. exposure time ; b) ln([m] 0 /[M] t ) vs. time, with [M] 0 and [M] t being the concentrations of monomers at time points zero and t, respectively; c) GPC traces at different polymerization times, THF employed as eluent. Note: The reactions were performed using a molar ratio of [Styrene]:[BTPA]:[fac-[Ir(ppy) 3 ]] = 200:1: and a 4.8 W blue LED lamp as light source in DMSO at room temperature. S31

32 End group characterization of polystyrene. Figure S19. 1 H NMR spectrum of PSt polymer synthesized by photoinduced living polymerization using BTPA and 4.8 W blue LED lamp as light source in DMSO during 36 h (M n, NMR = g/mol, M n, GPC =4 800 g/mol, monomer conversion 28%). Note: a) The reaction was performed using a molar ratio [St]:[BTPA]:[ fac-[ir(ppy) 3 ]] = 200:1: in DMSO at room temperature and a 4.8 W blue LED lamp as light source; b) Monomer conversion determined by 1 H NMR spectroscopy was calculated by the following equation: α = (1 - [(I 5.5ppm )/(I 3.6ppm /3)]) 100; c) Molecular weight and polydispersity determined by GPC analysis (THF used as eluent); d) Molecular weight determined by NMR analysis using M n, NMR = (I ppm /5)/(I 0.8ppm /3) MW St + MW BTPA, where I ppm and I 0.8ppm correspond to integrals of signal at ppm and 0.8 ppm attributed to phenyl group of St and methyl group of BTPA agent (Z-group). S32

33 RI response (a.u.) UV response (a.u.) Log(M) Figure S20. Comparison of molecular weight distributions recorded using a RI and UV (λ = 305 nm) detector for PSt synthesized by photoinduced living polymerization using BTPA and 4.8 W blue LED lamp as light source in DMSO during 36 h (M n, NMR = g/mol, M n, GPC =4 800 g/mol, monomer conversion 28%). S33

34 Part 4. Polymerization of unconjugated monomers, including vinyl acetate (VAc), vinyl pivalate (VP), N-vinyl pyrrolidinone (NVP) and dimethyl vinylphosphonate (DVP) by photoinduced living polymerization Figure S21. 1 H NMR spectrum of purified PVAc polymer synthesized by photoinduced living polymerization using xanthate and 4.8 W blue LED lamp as light source (M n, NMR = g/mol, M n, GPC = g/mol, monomer conversion 16%, Table 3, #3). S34

35 Figure S22. Comparison of molecular weight distributions recorded using a RI and UV (λ = 305 nm) detector for PVAc synthesized by photoinduced living polymerization using xanthate and 4.8 W blue LED lamp as light source in DMSO during 22 h (M n, NMR = g/mol, M n, GPC = g/mol, monomer conversion 76%, Table 3, #2). (a) S35

36 (b) (c) Figure S23. 1 H NMR spectrum of purified poly(vinyl pivalate) (PVP) (a), poly(n-vinyl pyrrolidinone) (PNVP) (b), and poly(dimethyl phosphonate) (PDVP) (c) synthesized by photoinduced living polymerization using xanthate and 4.8 W blue LED lamp as light source (Table 3, #7, 11, and 10). S36

37 Part 5. Synthesis of diblock copolymers using different monomer families Figure S24. GPC traces of PMMA macro-initiator and PMMA-b-PHPMA block copolymers synthesized by photoinduced living polymerization. (See Table 4, #4). DMAc as eluent. Figure S25. GPC traces of PHPMA macro-initiator and PHPMA-b-PMMA block copolymers synthesized by photoinduced living polymerization. (See Table 4, #7). DMAc as eluent. S37

38 Figure S26. (a) GPC traces of PSt macro-initiator and PSt-b-PMA block copolymers synthesized by photoinduced living polymerization. (See Table 4, #10), THF as eluent. PMA PMA-b-PDMA Retention Time (min) Figure S27. GPC traces of PMA macro-initiator and PMA-b-PDMA block copolymers synthesized by photoinduced living polymerization. (See Table 4, #12). DMAc as eluent. Figure S28. GPC traces of PMA macro-initiator and PMA-b-PSt block copolymer synthesized by photoinduced living polymerization. (See Table 4, #13). THF as eluent. S38

39 Figure S29. GPC traces of PDMA macro-initiator and PDMA-b-PMA block copolymer synthesized by photoinduced living polymerization. (See Table 4, #15). DMAc as eluent. Figure S30. GPC traces of PDMA macro-initiator and PDMA-b-PSt block copolymer synthesized by photoinduced living polymerization. (See Table 4, #16). DMAc as eluent. S39

40 Figure S31. GPC traces of PDMA macro-initiator and PDMA-b-PSt block copolymer synthesized by photoinduced living polymerization. (See Table 4, #18). DMAc as eluent. S40

41 Part 6. Synthesis of multi-block copolymers via photoinduced living polymerization. Table S5. Synthesis of decablock PMA polymers by an iterative approach to investigate the end-group fidelity. Experimental Conv. b Entry Conditions a (%) [M]:[BTPA] c d M n, th. M n, GPC (g/mol) (g/mol) End-group d M w /M n fidelity e SB1 88: SB2 73: SB3 58: SB4 82: SB5 62: SB6 96: SB7 127: SB8 120: SB9 76: SB10 144: Note 1: The successive chain extensions were not optimized. These data demonstrate the possibility to obtain high molecular weight multiblock copolymers using PET-RAFT polymerization. Note 2: a) The reactions were performed in DMSO at room temperature for 4h under 4.8 W Blue LED lamp as light source with an initial [Ir catalyst]/[ma] molar ratio of 5ppm. We did not add catalyst during the chain extension. After 5 chain extensions, the polymerization was diluted by addition of DMSO due to viscosity and carried out using MA/DMSO mixture of 25/75 (v/v); b) Monomer conversion determined by 1 H NMR spectroscopy was calculated by the following equation: α = (1 - [(I ppm /3)/(I 3.6ppm /3)]) 100; c) Theoretical molecular weight calculated using the following equation: M n, th = [MA] 0 /[BTPA] 0 MW MA α + MW BTPA, where [MA] 0, [BTPA] 0, MW MA, α and MW BTPA correspond to MA and BTPA concentration, molar mass of MA, monomer conversion and molar mass of BTPA; d) Molecular weight and polydispersity determined by GPC analysis (THF used as eluent). The molecular weights were recalculated using Mark-Houwing coefficients of PSt in THF (K = dl/g and α = 0.716) and PMA in THF (K = dl/g and α = 0.660); 2 e) End group fidelity was calculated by deconvolution of molecular weight distribution using previous methods S41

42 described in the literature. 4-6 Dead chains Living chains Molecular weight (g/mol) Figure S32. Number of chains versus molecular weight obtained by photoinduced living polymerization after 9 chain extensions. Note 1: To estimate the livingness according to GPC data, we first converted the molecular weight distributions to the corresponding number distributions (Figure S32). The y-axis values in the GPC distributions (normally what is given by the GPC software) are proportional to nm 2, where n is the number of chains and M is the molecular weight. 7 It follows that the number distribution, where the y-axis values are proportional to the number of chains, is given by w(log M)/M 2. Thus, if one plots w(log M)/M 2 vs M, the area under the curve between two given values of M is proportional to the number of chains within that range of M values. This calculation is estimated using the following hypothesis: the low molecular weight tails is attributed to dead polymers. S42

43 Part 7: Polymerization in the presence of air. (a) (b) Figure S33 Molecular weight distributions for photoinduced living polymerizations of MMA (a) and MA (b) in the presence of oxygen in DMSO. S43

44 Figure S34. 1 H NMR spectra for purified triblock copolymer PMA-b-PtBuA-b-PnBuA obtained by photoinduced living polymerization in the presence of air. S44

45 Table S6. Examples of polymers synthesized by photoinduced living polymerization mediated by Ru(bpy) 3 Cl 2 and Fluorescein in the presence of thiocarbonylthio compounds under 4.8 W blue LED light. a Monomer Initiating System Catalyst Concentrati on (ppm to Monomer) Time (h) Conv. b (%) M n, theoretical c (g/mol) M n, GPC d (g/mol) M w /M n MMA Ru(bpy) 3 Cl 2 /CPADB MA Ru(bpy) 3 Cl 2 /BTPA Styrene MMA MA Ru(bpy) 3 Cl 2 /BTPA Fluorescein/ CPADB Fluorescein/ BTPA Notes: CPADB: ; BTPA:. Molar ratios for polymerization: [monomer]/[cta]/[photocatalyst] = 1/0.005/(1~500 ppm). a) The reactions were performed in DMSO at room temperature; b) Monomer conversion determined by 1 H NMR spectroscopy; c) Theoretical molecular weight calculated using the following equation: M n, theo = [MA] 0 /[BTPA] 0 MW MA α + MW BTPA, where [MA] 0, [BTPA] 0, MW MA, α and MW BTPA correspond to MA and BTPA concentration, molar mass of MA, monomer conversion and molar mass of BTPA; or M n, th. = [MMA] 0 /[CPADB] 0 MW MMA α + MW CPADB, where [MMA] 0, [CPADB] 0, MW MMA, α and MW CPADB correspond to MMA and CPADB concentration, molar mass of MMA, monomer conversion and molar mass of CPADB; d) Molecular weight and polydispersity (M w /M n ) determined by GPC analysis (THF used as eluent). The molecular weights were recalculated using Mark-Houwing coefficients of PSt in THF (K = dl/g and α = 0.716) and PMA in THF (K = dl/g and α = 0.660). S45

46 Additional References (1) Boyer, C.; Liu, J.; Bulmus, V.; Davis, T. P. Aust. J. Chem. 2009, 62, 830. (2) Patrick, L.-D.; Alejandro-Magno, V.-H.; David, R. In Progress in Controlled Radical Polymerization: Mechanisms and Techniques; American Chemical Society: 2012; Vol. 1100, p 317. (3) Boyer, C.; Lacroix-Desmazes, P.; Robin, J.-J.; Boutevin, B. Macromolecules 2006, 39, (4) Boyer, C.; Soeriyadi, A. H.; Zetterlund, P. B.; Whittaker, M. R. Macromolecules 2011, 44, (5) Gody, G.; Maschmeyer, T.; Zetterlund, P. B.; Perrier, S. Macromolecules (6) Anastasaki, A.; Waldron, C.; Wilson, P.; Boyer, C.; Zetterlund, P. B.; Whittaker, M. R.; Haddleton, D. ACS Macro Lett. 2013, 2, 896. (7) Gilbert, R. G., 3, Trends Polym. Sci. 1995, 3, 222. S46