2 fluoroaniline

Triethylamine (BioUltra ≥ 99.5%, CAS 121-44-8), 3-chloroaniline (99%, CAS 108-42-9), cyclohexyl isocyanate (98%, CAS 3173-53-3), phenyl isocyanate (98%, CAS 103-71-9) manufactured by Sigma-Aldrich (St. Louis, MO, USA) were used without purifying.
4-(Trifluoromethoxy) isocyanate (97%, CAS 35037-73-1), aniline (99+%, CAS 62-53-3), 2-fluoroaniline (99%, CAS 348-54-9), 3-fluoroaniline (98%, CAS 372-19-0), 4-fluoroaniline (99%, CAS 371-40-4) produced by the AlfaAesar (Ward Hill, MA, USA) were used without additional purification.
Diethyl ether was purified by well-known methods. trans-4-Amino-(cyclohexyloxy)benzoic acid 7a [2 (link)], 1,3-dehydroadamantane 2a [12 (link)], 1,3-dehydro-5,7-dimethyladamantane 2b [12 (link)], 2-(adamantane-1-yl)-2-phenylacetic acid ethyl ester 3a [15 (link)], 2-(adamantane-1-yl)-2-phenylacetic acid 4a, 1-(isocyanato(phenyl) methyl)adamantane 5a [10 (link)] were obtained by well-known methods.

Polymer-wrapped SWNTs were functionalized with a range of commercially available aryl compounds (2-iodoaniline, 2-bromoaniline, 2-fluoroaniline, 5-fluoro-2-iodoaniline, 2-iodophenol, thiophenol, indole; used as received from Sigma Aldrich, ≥97%). For a step-by-step protocol, refer to Supplementary Methods 1. Briefly, an appropriate amount of aryl reagent was dissolved in toluene to achieve a final reaction concentration of 29.30 mmol L⁻¹. DMSO (anhydrous) and KO^tBu (Sigma Aldrich, 98%) dissolved in THF (anhydrous) were added to this solution. Finally, an enriched SWNT dispersion in toluene was added to the mixture such that the SWNT concentration in the reaction mixture corresponded to an optical density of 0.3 cm⁻¹ at the E₁₁ transition. The final solvent composition was 83.3 : 8.3 : 8.3 vol-% toluene/DMSO/THF. Functionalization was performed in the dark or under illumination with UV-light (LED SOLIS-365C, Thorlabs, 365 nm, 1.9 mW mm⁻²) at room temperature. The reaction was stopped after a given time by vacuum filtration of the reaction mixture through a PTFE membrane filter (0.1 μm pore size). The collected SWNTs were washed with methanol and toluene to remove unreacted reagents and side products. The resulting filter cake was redispersed by bath sonication in toluene with fresh wrapping polymer for stabilization.

For our investigation, we used the same compounds as for Paper-LTPI^{28 (link)} and in a comparison between Paper-LTPI, ESI and APCI^{27 (link)}: 3-aminophenol, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-methoxyaniline (o-anisidine), 3-methoxyaniline (m-anisidine), 4-methoxyaniline (p-anisidine), 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 3-methylaniline (m-toluidine), 3-aminoaniline (m-phenylenediamine), 4-aminoaniline (p-phenylenediamine), 2-aminobenzonitrile, 3-aminobenzonitrile and 4-aminobenzonitrile from Sigma Aldrich (Taufkirchen, Germany); 2-methylaniline (o-toluidine), 4-methylaniline (p-toluidine) from Fluka (Buchs, Switzerland) and aniline from Acros (Geel, Belgium). Acetonitrile (ACN, LC–MS grade) was from VWR (Dresden, Germany) and water (LC–MS grade) from BIOSOLVE (Valkenswaard, Netherlands). 2-aminoaniline (o-phenylenediamine), 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-aminophenol, 4-aminophenol, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, sulfanilic acid and 4-chloroaniline were kindly provided by Prof. em. S. Berger (University of Leipzig, Germany).