Compound 9
9-([1,1'-Biphenyl]-4-yl)-2,7-bis((2,5-bis(octyloxy)-4-((triisopropylsilyl)buta-1,3-diyn-1-yl)phenyl)ethynyl)-9H-carbazole
From: Fluctuating exciton localization in giant π-conjugated spoked-wheel macrocycles
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InChIKey UGNVRGSZFRADIK-UHFFFAOYSA-N
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
A solution of CuI (19.0 mg, 100.0 µmol), I2 (42.2 mg, 166.6 µmol), Pd(PPh3)2Cl2 (35.2 mg, 50.0 µmol), THF (15 mL), and diisopropyl amine (10 mL) was purged with air for 60 min. Then the solution was heated to 50 °C and a solution of 9-([1,1'-biphenyl]-4-yl)-2,7-bis((4-ethynyl-2,5-bis(octyloxy)phenyl)ethynyl)-9H-carbazole (45.0 mg, 41.7 µmol) and triisopropylsilyl acetylene (3.0 mg, 16.7 µmol) in THF (5 mL) was added under vigorous stirring. After 150 min, triisopropylsilyl acetylene (570.0 mg, 3123.5 µmol, 0.7 mL) was added and stirring was continued for 10 min at 50 °C. The reaction was allowed to cool to r.t., diluted with chloroform and washed with aq. H2SO4 (10 %), water, and brine. After drying over MgSO4 and removal of the solvent, the crude product was fractioned by Soxhlet extraction (methanol, acetone, diethyl ether, dichloromethane, and chloroform). The catalyst and 1,4‑bis(triisopropylsilyl)buta-1,3-diyne were washed out with methanol. The monomer (9), along with some of the dimer (10) and the trimer, was found in the acetone fraction, while all higher oligomers (including 11) had been eluted with dichloromethane. The chloroform fraction contained some polymeric material. The acetone (12 mg), the dichloromethane (39 mg) and the chloroform (10 mg) fractions were further separated by recGPC. The carbazole-based oligomers 9, 10, and 11 were obtained as yellow solids.Compound 9 (linear monomer)(2.8 mg, 1.943 µmol, 5 %) 1H NMR (400 MHz, CDCl3, 298 K) δ [ppm] = 8.13 – 8.05 (m, 2 H), 7.89 – 7.81 (m, 2 H), 7.73 – 7.60 (m, 6 H), 7.56 – 7.39 (m, 5 H), 7.00 – 6.93 (m, 4 H), 4.06 – 3.91 (m, 8 H), 1.90 – 1.74 (m, 8 H), 1.53 – 1.40 (m, 8 H), 1.40 – 1.16 (m, 32 H), 1.11 (s, 42 H), 0.97 – 0.77 (m, 12 H).MS (MALDI-TOF, DCTB) (calcd. for C98H129NO4Si2 monoisotopic: 1439.95, distr. max.: 1441.25): m/z 1439.9 [M]+; GPC (in THF vs. PS): Mp = 2060 g mol‑1.
