Molecules 2011, 16
5780
0.75–0.95 (m, 3H), 1.12–1.42 (m, 16H), 1.58–1.72 (m, 2H), 1.96–2.08 (m, 4H), 2.63 (t, 2H, J = 7.6 Hz),
4.49–4.54 (m, 2H), 4.59–4.64 (m, 2H), 5.30–5.40 (m, 2H), 6.83–6.93 (m, 3H), 7.24–7.27 (m, 1H), 7.33
(d, 2H, J = 8.6 Hz), 7.71–7.81 (m, 9H), 8.13 (d, 2H, J = 8.6 Hz), 8.19–8.24 (m, 6H), 8.82–8.89 (m, 8H);
13C-NMR (CDCl3): δ 14.6, 23.1, 27.6, 27.7, 29.5, 29.7, 29.7, 29.8, 29.9, 30.1, 30.2, 31.7, 31.9, 32.2,
36.3, 66.9, 67.2, 112.0, 112.9, 113.3, 115.5, 115.7, 120.4, 120.5, 120.6, 121.4, 121.8, 127.1, 128.1,
128.4, 129.7, 129.8, 130.3, 130.4, 135.0, 135.3, 136.0, 142.6, 142.6, 145.3, 155.8, 158.9, 159.1; FTIR
(neat), v/cm−1: 3317, 3006, 2923, 2852, 1598, 1583, 1508, 1470, 1441, 1350, 1244, 1175, 1157, 1109,
1072, 1032, 1001, 979, 966, 932, 909, 876, 845, 800, 731; UV-Vis (CH2Cl2) λmax, nm: 419, 516, 552,
590, 646; MALDI-TOF MS m/z: 958 [M]+; Molecular weight: 958 amu; Anal. Calc. for C67H66N4O2:
C, 83.41; H, 7.02; N, 6.91. Found: C, 83.84; H, 6.88; N, 5.84%.
3.3.3. Synthesis and characterization of 5,15-diphenyl-10, 20-di-4-(2-(3-pentadec-8-enyl)phenoxy)ethoxy]
phenyl porphyrin (4)
Aldehyde 1 (0.45g, 1 mmol) and meso-phenyldipyrrole 2 (0.22g, 1 mmol) in chloroform (150 mL)
were stirred at room temperature for 10 min, and then BF3·OEt2 (3.75 mL of 0.1 M solution in CHCl3,
0.375 mmol) was added. The reaction mixture was stirred at room temperature for 24 h, then DDQ
(0.17 g in CHCl3) was added slowly to the solution with vigorous stirring. Subsequently, the reaction
mixture was stirred at room temperature for a further 24 h and then removed the solvent under vacuum.
The reaction mixture was passed through a silica gel chromatography column (CH2Cl2/hexane 6/4 v/v).
Yield: 15%; 1H-NMR (CDCl3): δ −2.76 (br, s, 2H), 0.80–0.95 (m, 6H), 1.16–1.46 (m, 32H), 1.58–1.72
(m, 4H), 1.96–2.12 (m, 8H), 2.64 (t, 4H, J = 7.7 Hz), 4.53 (t, 4H, J = 4.5Hz), 4.63 (t, 4H, J = 4.5 Hz),
5.28–5.42 (m, 4H), 6.83–6.94 (m, 6H), 7.24–7.30 (m, 2H), 7.34 (d, 4H, J = 8.7 Hz), 7.72–7.82 (m, 6H),
8.14 (d, 4H, J = 8.7 Hz), 8.22 (d, 4H, J = 7.4 Hz), 8.84 (d, 4H, J = 4.5 Hz), 8.87 (d, 4H, J = 4.7 Hz);
13C-NMR (CDCl3): δ 14.3, 14.6, 23.1, 23.3, 26.0, 26.1, 27.7, 27.7, 29.4, 29.7, 29.7, 29.8, 29.8, 29.8,
29.8, 29.9, 30.1, 30.1, 30.1, 30.1, 30.2, 31.9, 32.0, 32.2, 36.5, 66.9, 67.3, 112.0, 113.3, 115.5, 120.2,
120.3, 120.4, 120.5, 121.8, 127.1, 128.1, 128.4, 128.6, 129.7, 130.3, 130.4, 130.4, 130.6, 135.0, 135.4,
135.4, 136.0, 142.7, 142.7, 145.2, 145.2, 158.9, 159.2; FTIR (neat), v/cm−1: 3317, 3006, 2923, 2853,
1727, 1602, 1583, 1508, 1454, 1401, 1376, 1350, 1245, 1174, 1158, 1111, 1072, 1001, 980, 966, 932,
907, 876, 844, 801, 733; UV-Vis (CH2Cl2) λmax, nm: 420, 517, 553, 591, 647; MALDI-TOF MS m/z:
1303 [M]+; Molecular weight: 1303 amu; Anal. Calc. for C90H102N4O4: C, 82.61; H, 7.74; N, 4.51.
Found: C, 82.95; H, 7.83; N, 4.30%.
3.3.4. General procedure for the synthesis of 3a–3c, 4a–4c
Porphyrin 3 (30.0 mg, 0.031 mmol) or 4 (30.0 mg, 0.023 mmol) were dissolved in CHCl3 (20 mL).
To this solution was added an excess of Zn(CH3COO)2 (34.0 mg, 0.186 mmol), CuCl2 (20.0 mg,
0.186 mmol) or Co(CH3COO)2·4H2O (46.3 mg, 0.186 mmol), and the mixture was stirred at room
temperature. The reaction was checked by TLC. After disappearance of 3 or 4, the solution was filtered
and then the solvent was removed under vacuum. The crude product was purified by silica gel
chromatography (CHCl3/Hexane, 7/3 v/v) to give 3a, 3b, 3c, 4a, 4b, 4c in nearly quantitative yields.