Compound 4
4-(((4-((4'-(2-((4-(((3-Cyanopropyl)diisopropylsilyl)ethynyl)-2,5-bis(octyloxy)phenyl)ethynyl)-7-((4-(((3-isocyanopropyl)diisopropylsilyl)ethynyl)-2,5-bis(octyloxy)phenyl)ethynyl)-9H-carbazol-9-yl)-[1,1'-biphenyl]-4-yl)ethynyl)-2,5-bis(octyloxy)phenyl)ethynyl)dimethylsilyl)butanenitrile
From: Fluctuating exciton localization in giant π-conjugated spoked-wheel macrocycles
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InChIKey BQJPPYYIGBYJRT-UHFFFAOYSA-N
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
2 (608 mg, 471 µmol), 3 (487 mg, 659 µmol) and 2-di-t-butylphosphino-2′,4′,6′-triisopropylbiphenyl (tBu-XPhos) (120 mg, 283 µmol) were dissolved in toluene (20 mL) and heated to 80 °C. After 5 min, a mixture of Pd2dba3(86 mg, 94 µmol) and NaOtBu (82 mg, 848 µmol) was added at 80 °C under argon flow. After 1 h, the reaction was cooled to r.t., diluted with MTBE, and washed with aq. H2SO4 (10 %), water, and brine. Drying over MgSO4 and concentration in vacuo gave the crude product that was purified by column chromatography (CH:DCM = 4:3) and recGPC. 4 (603 mg, 309 µmol, 66 %) was obtained as a yellow oil. 1H NMR (400 MHz, CDCl3, 298 K) δ [ppm] = 8.09 (d, 3JH,H = 8.1 Hz, 2 H), 7.93 – 7.83 (m, 2 H), 7.75 – 7.60 (m, 8 H), 7.55 – 7.46 (m, 2 H), 7.01 (s, 1 H), 6.99 – 6.95 (m, 3 H), 6.94 (s, 2 H), 4.09 – 3.99 (m, 8 H), 3.96 (t, 3JH,H = 6.4 Hz, 4 H), 2.51 – 2.39 (m, 6 H), 1.98 – 1.73 (m, 18 H), 1.68 – 1.44 (m, 12 H), 1.44 – 1.17 (m, 48 H), 1.17 – 1.02 (m, 28 H), 0.98 – 0.78 (m, 24 H), 0.33 – 0.26 (m, 6 H); 13C NMR (101 MHz, CDCl3, 298 K) δ [ppm] = 154.36, 154.20, 153.48, 153.37, 141.17, 139.92, 139.76, 136.38, 132.21, 128.50, 127.56, 126.93, 124.11, 123.12, 122.91, 121.11, 120.42, 119.75, 119.70, 117.64, 117.31, 116.61, 116.11, 114.55, 114.49, 113.26, 113.18, 113.04, 103.89, 102.57, 97.88, 96.07, 95.12, 94.73, 86.98, 86.18, 69.74, 69.64, 69.33, 69.14, 31.84, 31.80, 31.74, 29.39, 29.37, 29.33, 29.30, 29.27, 29.26, 29.23, 26.08, 26.07, 25.99, 25.96, 22.67, 22.66, 22.65, 22.63, 22.60, 21.27, 20.73, 20.69, 20.65, 20.44, 18.22, 17.98, 15.73, 14.10, 14.07, 14.05, 11.78, 9.61, -1.80; MS (MALDI-TOF, DCTB) (calcd. for C128H174N4O6Si3 monoisotopic: 1947.27, distr. max.: 1949.03): m/z 2197.3 [M+DCTB]+, 1947.2 [M]+; GPC (in THF vs. PS): Mp = 2840 g mol-1.
