Institute of Molecular Sciences, UMR-CNRS 5255, University of Bordeaux 351 Cours de la libération, Talence cedex, France

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1 Poly(arylene vinylene) Synthesis via a Precursor Step-growth Polymerization Route Involving the Ramberg-Bäcklund Reaction as Key Post-chemical Modification Step Kunche Aravindu 1,2, Eric Cloutet 2, Cyril Brochon 2, Georges Hadziioannou 2, Joan Vignolle, Frédéric Robert 1, Daniel Taton 2,* Yannick Landais 1 * 1 Institute of Molecular Sciences, UMR-CNRS 5255, University of Bordeaux 351 Cours de la libération, Talence cedex, France 2 Laboratoire de Chimie des Polymères Organiques (LCPO UMR 5629), CNRS-Université de Bordeaux-Bordeaux INP, 16 Avenue Pey-Berland, Pessac cedex, France S1

2 Table S1. Optimization of step-growth polymerization and synthesis of PF-S. Effect of Base on the polymerization a Br C 6 H 13 C 6 H 13 Br + HS C 6 H 13 C 6 H 13 SH Base, solvent T( C), time C 6 H 13 C 6 H 13 S n F-Br F-SH PF-S Entry Base Yield (%) n (g/mol) w (g/mol) Ð b 1 Et3N traces 3,000 4, DIPEA TMG ,300 25, KOH c 78 12,000 17, a All reactions were carried out on a 0.1 mmol scale, F-Br (1 equiv.), F-SH (1 equiv.), base (3 equiv.) in THF (0.2 M) for 14 h at 100 C in a sealed tube. b Determined by SEC in THF on the basis of a polystyrene calibration. c THF/MeOH (0.2 M) was used as a solvent. Table S2. Optimization of step-growth polymerization and synthesis of PF-S. Effect of Temperature on the polymerization a Entry Temp ( C) Yield (%) n (g/mol) w (g/mol) Ð b 1 RT 64 15,000 74, ,800 53, ,000 17, ,400 52, a All reactions were carried out on 0.1 mmol scale, F-Br (1 equiv.), F-SH (1 equiv.), KOH (3 equiv.) in THF/MeOH (0.2 M) for 14 h in a sealed tube. b Determined by SEC in THF on the basis of a polystyrene calibration. S2

3 Table S3. Optimization of step-growth polymerization and synthesis of PF-S. Effect of Time on the polymerization a Entry Time (h) Yield (%) n (g/mol) w (g/mol) Ð b ,100 60, ,000 57, ,000 75, a All reactions were carried out on 0.1 mmol scale, F-Br (1 equiv.), F-SH (1 equiv.), KOH (3 equiv.) in THF/MeOH (0.2 M) for 14 h in a sealed tube. b Determined by SEC in THF on the basis of a polystyrene calibration. Table S4. Optimization of step-growth polymerization and synthesis of PF-S. Effect of Solvent on the polymerization a Entry Solvent Temp ( C) Yield (%) n (g/mol) w (g/mol) Ð b 1 DMAc RT 45 41, , DMAc ,000 7, DMF ,000 6, THF/MeOH ,000 17, a All reactions were carried out on 0.1 mmol scale, F-Br (1 equiv.), F-SH (1 equiv.), KOH (3 equiv.) in THF/MeOH (0.2 M) for 14 h in a sealed tube. b Determined by SEC in THF on the basis of a polystyrene calibration. S3

4 Transmittance (normalized) (i) S=O PF-S PF-SO PFV (ii) Wavenumber (cm -1 ) Transmittance (normalized) S=O PFC-S PFC-SO PFCV Wavenumber (cm -1 ) Figure S1. IR spectra of (i) PF-S, PF-SO and PFV (ii) PFC-S, PFC-SO and PFCV In order to prevent further polymer degradation, we followed the same protocol as for the synthesis of PF-S, but we quenched the reaction with an excess amount (10 equiv.) of benzyl mercaptan to obtain PFS-Q in 79% yield (Scheme 1). Subsequent oxidation with m-cpba (PF-SOQ, 71% yield), followed by Ramberg-Bäcklund reaction gave the PFVQ in 53% yield. Concerning the PFS quenched with benzyl mercaptan (PFS-Q) and the corresponding PF-SO and PFV (respectively PF-SOQ, and PFVQ), obtained molecular weight are very similar and the same behavior is observed after sulfonation. SEC results are shown in Figure S2 and Table S5. Optical properties of PF-SQ, PF-SOQ and PFVQ were analyzed by UV vis absorption and emission spectra as shown in Figure S3 and S4. S4

5 Scheme S1. Synthesis of end-chained PFV (PFVQ) 1,0 0,8 PF-SQ PF-SOQ PFVQ Normalized response 0,6 0,4 0,2 0, Retention time (min) Figure S2. SEC analysis of PF-SQ, PF-SOQ and PFVQ Table 5. SEC analysis of PF-SQ, PF-SOQ and PFVQ Polymer Mn Mw Ð PF-SQ 8,000 21, PF-SOQ 11,000 25, PFVQ 8,200 27, S5

6 Absorbance (normalized) 1,0 0,8 0,6 0,4 PF-SQ PF-SOQ PF-VQ 0,2 0, Wavelength (nm) Figure S3. UV vis absorption of PF-SQ, PF-SOQ and PFVQ 8x10 5 (a) (b) Intensity (a. u.) 4x10 5 Intensity (a. u.) 2x10 5 8x x10 6 (c) Wavelength (nm) 0 1x Wavelength (nm) (d) Intensity (a. u.) 5x10 5 Intensity (a. u.) 5x Wavelength (nm) Wavelength (nm) Figure S4. Emission spectra of PFVQ (a) excited at 425 nm (b) excited at 450 nm in CHCl3 (c) excited at 425 nm (d) excited at 450 nm on thin-film S6

7 The two conjugated polymers PFVCV and PFV were also measured in solid film, obtained by drop casting from chloroform solution. (Figure S5). Figure S5. UV vis absorption of PFVCV and PFV in solid thin film. The thermal stability of PF-S, PF-SO, PFV & PFVCV was analyzed by TGA (Figure S6). Weight loss (%) (a) PF-S PF-SO PFV Weight loss (%) (b) Temperature ( C) Temperature ( C) PFV PFCV Figure S6. TGA thermograms of: (a) PF-S, PF-SO, and PFV; (b) PFV and PFVCV (condition: 60 ml/min N2 flow and heating rate of 10 C/ min). S7

8 Figure S7. PFC raw analysis of SEC traces (see also Figure 5) S8

9 Figure S8. PFC-SO raw analysis of SEC traces (see also Figure 5) S9

10 Figure S9. PFV-CV raw analysis of SEC traces (see also Figure 5) S10

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