Compound 1
Spoked Carbazole Wheel
From: Fluctuating exciton localization in giant π-conjugated spoked-wheel macrocycles
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InChIKey OLOFASSBCMXXDL-UHFFFAOYSA-N
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
A solution of THF (45 mL) and diisopropyl amine (50 mL) was purged with air for 60 min prior to the addition of CuI (8.6 mg, 45.2 µmol), I2 (17.2 mg, 67.8 µmol), and Pd(PPh3)2Cl2 (21.2 mg, 30.1 µmol). The catalyst solution was heated to 50 °C and a solution of 8 (35.0 mg, 3.77 µmol) in THF (30 mL) was added with a constant rate over 60 h under vigorous stirring. After cooling to r.t., the reaction was diluted with toluene and concentrated in vacuo. Then the residue was redissolved in dichloromethane and washed with aq. H2SO4 (10 %), water, and brine. After drying over MgSO4 and removal of the solvent, the crude product was purified by flash chromatography (CH:DCM = 1:2) and recGPC. 1 (19.0 mg, 2.0 µmol, 54 %) was obtained as a yellow solid. 1H NMR (500 MHz, CDCl3, 298 K) δ [ppm] = 8.10 (d, 3JH,H = 8.0 Hz, 12 H), 7.87 (d, 3JH,H = 8.4 Hz, 12 H), 7.76 – 7.60 (m, 48 H), 7.52 – 7.41 (m, 12 H), 7.15 (d, 3JH,H = 8.1 Hz, 12 H), 7.02 (s, 6 H), 7.01 – 6.98 (m, 18 H), 6.97 (s, 12 H), 6.84 (d, 3JH,H = 8.1 Hz, 12 H), 4.11 – 3.88 (m, 72 H), 1.97 – 1.71 (m, 72 H), 1.69 – 1.08 (m, 360 H), 0.98 – 0.74 (m, 108 H); 13C NMR (126 MHz, CDCl3, 298 K) δ [ppm] = 155.24, 153.73, 153.65, 153.59, 141.41, 140.16, 139.76, 136.42, 132.35, 131.46, 130.60, 128.64, 127.80, 127.03, 123.37, 123.24, 121.28, 120.90, 120.80, 117.84, 117.09, 117.00, 116.93, 115.35, 114.32, 114.25, 113.70, 112.70, 96.88, 95.29, 94.67, 87.39, 86.42, 86.19, 79.76, 79.60, 79.56, 69.91, 69.78, 69.70, 69.67, 31.97, 31.94, 31.88, 29.53, 29.51, 29.46, 29.43, 29.39, 29.37, 29.30, 29.28, 29.27, 26.24, 26.14, 26.07, 26.01, 22.86, 22.84, 22.81, 22.78, 14.35, 14.28, 14.26, 14.22; MS (MALDI-TOF, DCTB) (calcd. for C654H756N6O36 monoisotopic: 9269.75, distr. max.: 9277.02): m/z 10017.8 [M+3*DCTB]+, 9777.8 [M+2*DCTB]+, 9527.5 [M+DCTB]+, 9777.8 [M]+; GPC (in THF vs. PS): Mp = 9940 g mol-1.
