SUPPLEMENTARY INFORMATION

Conjugated Fluorene Moiety-Containing Comb-Like Polymers for Dispersion of Single

Wall Carbon Nanotubes: Polymer Wrapping Abilities and Electrical Properties

Hsuan-Chun Chang,1,‡ Jau-Tzeng Wang,1, ‡ Dian-Han Li,1 Chien Lu,1 Han-Wen Hsu,2 Hung-

Chin Wu,1 Cheng-Liang Liu,2 and Wen-Chang Chen1,*

1Department of Chemical Engineering, National Taiwan University, Taipei, 10617 Taiwan.

2Department of Chemical and Materials Engineering, National Central University, Taoyuan,

32001 Taiwan.

‡These authors contributed equally to this work.

Correspondence: Professor W.-C. Chen, Department of Chemical Engineering, National

Taiwan University, Taipei, 10617 Taiwan. E-mail: chenwc@ntu.edu.tw

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Synthesis of fluorene-based monomer:

2-Bromo-9,9-di-n-hexylfluorene (1):

1-Bromohexane (50.3 ml, 357.0 mmol) was added to a mixture of 2-bromofluorene (25.0 g,

102.0 mmol) and tetrabutylammonium bromide (3.3 g, 10.2 mmol) in DMSO (250 ml) and

50% (w/w) aqueous NaOH (35 mL). The reaction mixture was stirred at 70 °C for overnight

and then poured into a large excess of ethyl acetate. After filtration to remove precipitated

NaOH, the organic layer was washed with dilute 2N HCl, brine, and then dried over

anhydrous MgSO4. After filtration, the solvents were removed by evaporation, and the crude

product was purified by chromatography on silica gel with hexane as eluent to obtain a light

yellow oil (32.6 g, yield: 77.5%). 1H NMR (CDCl3): δ(ppm) = 7.64 (m, 1H), 7.54 (d, 1H),

7.43 (m, 2H), 7.31 (d, 3H), 1.93 (m, 4H), 1.08 (m, 12H), 0.77 (m, 6H), 0.60 (m, 4H), as

shwon in Figure S10(a))

9,9-Di-n-hexylfluorenyl-2-boronic acid (2):

2-bromo-9,9-dihexylfluorene (20.0 g, 48.6 mmol) was dissolved in anhydrous THF (250 ml)

first, then n-BuLi (2.5 M in hexane, 27.5 ml, 68 mmol) was slowly added at -78 °C. After 60

min, tri(isopropyl) borate (57 ml, 247 mmol) was added by syringe. The mixture was allowed

to warm to room temperature slowly and stirred for overnight. HCl (2N, 200 ml) was added

to the stirred solution while maintaining the solution at 0 oC for 1 h. The organic layer was

washed with water and dried over anhydrous MgSO4 and the water layer was extracted with

2

diethyl ether (200 mL). The combined ether layers were washed twice with brine (100 ml)

and were dried over anhydrous MgSO4. After filtration, the solvent was removed under

reduced pressure, the crude product was purified by column chromatography on silica gel by

using hexane as eluent to obtain a white solid (15.5 g, yield: 84 %). 1H NMR (CDCl3): δ

(ppm) = 8.32 (d, 1H), 8.23 (s, 1H), 7.89 (d, 1H), 7.83-7.81 (m, 1H), 7.79-7.53 (m, 2H), 7.42-

7.37 (m, 3H), 2.14-2.04 (m, 4H), 1.14-1.04 (m, 12H), 0.77-0.5 (m, 10H), as shwon in Figure

S10(b)).

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Figure S1 GPC profiles of the synthesized P2VPn-co-P(St-Fl)m copolymers 3a, 4a, and 5a.

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Figure S2 1H NMR spectra of (a) 3b, (b) 4b, and (c) 5b in CD2Cl2.

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Figure S3 GPC profiles of (a) 3b, 4b, and 5b and (b) 6 and 7.

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Figure S4 1H NMR spectra of (a) 6 and (b) 7 in CD2Cl2.

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Figure S5 TGA curves of 5a, 5b, and 7 at a heating rate of 20 oC min-1 under nitrogen atmosphere.

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Figure S6 DSC curves of 5a, 5b, and 7 at a heating rate of 10 oC min-1 under nitrogen atmosphere.

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Figure S7 Schematic illustration of dispersing SWNTs by P2VP-co-P(St-Fl)comb-like

copolymers.

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Figure S8 AFM images of 5a/SWNTs network after removing the polymer at 500 °C.

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Figure S9 Transfer characteristics of SWNTs FETs prepared from 5a wrapped SWNTs solution.

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Figure S10 1H NMR spectra of (a) 1 and (b) 2 in CDCl3.

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