ACCEPTED MANUSCRIPT
A mixture of compound 9 (1.9 g, 1.7 mmol) and 2-methyl-3-butyn-2-ol (0.43 g, 5.1 mmol)
was dissolved in dry THF (20 mL) and dry triethylamine (20 mL) under a nitrogen atmosphere.
Then Pd(PPh3)4 (0.01 g, 0.01 mmol) and CuI (0.002 g, 0.01 mmol) were added, and the mixture
was stirred over night at 25 °C. The solvent was evaporated to dryness and purified by column
chromatography on silica gel using petroleum ether/ethyl acetate (10 : 1) as the eluent to afford
compound 10 as a yellow solid. Yield: 76% (1.4 g, 1.3 mmol). m.p. 48-49 °C. 1H NMR (CDCl3,
400 MHz), δ (ppm): 7.49 (d, J = 7.2 Hz, 2H, 2×PhH), 7.11 (t, J = 2.6 Hz, 1H, ThiopheneH), 7.04
(t, J = 1.8 Hz, 1H, ThiopheneH), 6.97 (d, J = 7.2 Hz, 2H, 2×PhH), 6.62 (s, 2H, 2×PhH), 4.97 (s,
2H, OCH2), 3.99-3.93 (m, 6H, 3×OCH2), 2.03 (s, 1H, OH), 1.81-1.72 (m, 6H, 3×OCH2CH2), 1.62
(s, 6H, 2×CH3), 1.47-1.43 (m, 6H, 3×OCH2CH2CH2), 1.30-1.24 (m, 72H, 36×CH2), 0.86 (t, J =
6.0 Hz, 9H, 3×CH3). 13C NMR (CDCl3, 100 MHz), δ (ppm): 158.8 (1 C), 153.4 (2 C), 145.6 (1C),
138.1 (1 C), 133.1 (1 C), 131.6 (1 C), 127.1 (2 C), 126.8 (1 C), 121.8 (1 C), 120.8 (1 C), 115.3 (2
C),106.1 (2 C), 97.8 (1 C), 75.8 (1 C), 73.5 (1C), 70.6 (1C), 69.2 (2 C), 65.8 (1 C), 32.0-14.1
(multi-carbon in alkyl chain); Elemental Analysis, found: C, 78.33; H, 10.85%; molecular formula
C70H116O5S requires C, 78.59; H, 10.93%. FTIR (KBr, cm-1) 3663, 2918, 2860, 1600, 1504, 1459,
1376, 1233, 1117, 800, 701.
2.2.5. 2-ethynyl-5-(4-((3,4,5-tris(hexadecyloxy)benzyl)oxy)phenyl)thiophene (11)
To a mixture of compound 10 (1.2 g, 1.1 mmol) and KOH (0.19 g, 3.4 mmol), toluene (40 mL)
was added. The mixture was heated under reflux for 4 h. The solution was filtered and purified by
column chromatography on silica gel using hexane as the eluent to afford 2-ethynyl-5-
(4-((3,4,5-tris(hexadecyloxy)benzyl)oxy)phenyl)thiophene 11 as a yellow solid. Yield: 72% (0.8 g,
0.79 mmol). m.p. 52-53 °C. 1H NMR (CDCl3, 400 MHz), δ (ppm): 7.50 (d, J = 8.8 Hz, 2H,
2×PhH), 7.21 (d, J = 4 Hz, 1H, ThiopheneH), 7.05 (d, J = 3.6 Hz, 1H, ThiopheneH), 6.98 (d, J =
8.4 Hz, 2H, 2×PhH), 6.62 (s, 2H, 2×PhH), 4.97 (s, 2H, OCH2), 3.99-3.93 (m, 6H, 3×OCH2), 3.38
(s, 1H, C≡CH), 1.82-1.71 (m, 6H, 3×OCH2CH2), 1.47-1.43 (m, 6H, 3×OCH2CH2CH2), 1.29-1.23
(m, 72H, 36×CH2), 0.88 (t, J = 6.6 Hz, 9H, 3×CH3). 13C NMR (CDCl3, 100 MHz), δ (ppm): 158.9
(1 C), 153.4 (2 C), 145.6 (1 C), 138.1 (1C), 134.2 (1 C), 131.5 (1 C), 127.3 (2 C), 126.7 (1 C),
121.8 (1 C), 120.1 (1 C), 115.4(2 C), 106.1 (2 C), 81.6 (2 C), 73.5 (1C), 70.6 (1C), 69.2 (2 C),
31.9-14.1 (multi-carbon in alkyl chain); Elemental Analysis, found: C, 79.32; H, 10.85%;
molecular formula C67H110O4S requires C, 79.55; H, 10.96%. FTIR (KBr, cm-1) 3305, 2918, 2850,
1589, 1503, 1433, 1378, 1241, 1116, 800, 718.
2.2.6. 4,7-bis((5-(4-((3,4,5-tris(hexadecyloxy)benzyl)oxy)phenyl)thiophen-2-yl)ethynyl)benzo[1,2,
5] thiadiazole I
Dry Et3N (15 mL), 4,7-dibromobenzothiadiazole 3 (0.1 g, 0.34 mmol), CuI (0.004 g, 0.02
mmol), PPh3 (0.005 g, 0.02 mmol) and Pd(PPh3)2Cl2 (0.025 g, 0.02 mmol) were placed in a flask
and degassed with nitrogen, then compound 11 (0.7 g, 0.69 mmol) was added, and the mixture
was maintained at 50 °C for 18 h. The solvent was evaporated to dryness, and the crude product
was purified by column chromatography on silica gel using petroleum ether : dichloromethane (2 :
1
1) as the eluent to afford compound I as a red solid. Yield: 70% (0.45 g, 0.21 mmol). H NMR
(CDCl3, 400 MHz), δ (ppm): 7.76 (s, 2H, 2×PhH), 7.55 (d, J = 8.4 Hz, 4H, 4×PhH), 7.40 (d, J =
3.6 Hz, 2H, 2×ThiopheneH), 7.16 (d, J = 3.6 Hz, 2H, 2×ThiopheneH), 7.00 (d, J = 8.8 Hz, 4H,
4×PhH), 6.63 (s, 4H, 4×PhH), 4.99 (s, 4H, 2×OCH2), 4.00-3.94 (m, 12H, 6× OCH2), 1.83-1.73 (m,
12H, 6×OCH2CH2), 1.49-1.43 (m, 12H, 6×OCH2CH2CH2), 1.34-1.23 (m, 144H, 72×CH2), 0.88 (t,