FUSED p-EXTENDED DISCOTIC TRIANGULAR PORPHYRINOIDS
567
1 eq) 4-bromobenzaldehyde (11) were dissolved in 4 mL
anhydrous THF under argon atmosphere. To this solution
16 mL diisopropylamine, 15 mg (13 µmol, 10%mol)
Pd(PPh3)4 and 5 mg (26 µmol, 20%mol) CuI were added.
The reaction mixture was heated to 60 °C and stirred for
3 h at this temperature. The reaction mixture was filtered
over a frit and the solvent removed in vacuo. The crude
product was purified by column chromatography using
hexane:DCM (2:1) as eluent, affording 255 mg (60%,
0.68 mmol) of compound 6 as a colorless liquid. 1H NMR
(CD2Cl2, 300 MHz, 298 K): d, ppm 0.88 (t, 3J = 7.0 Hz,
UV-vis (CHCl3, 10-5 M): λmax, nm 343. 1H NMR (C3D2F6O
plus 0.1% C2DF3O2, 700 MHz, 298 K): d, ppm 0.74 (m,
9H), 1.14 (m, 54H), 1.50 (m, 6H), 2.54 (m, 6H), 6.09 (d,
6H), 6.15 (d, 6H), 6.62 (s, 6H), 6.92 (d, 3J = 7.3 Hz, 6H),
7.11 (d, 3J = 7.3 Hz, 6H). 13C NMR (C3D2F6O plus 0.1%
C2DF3O2, 176 MHz, 298 K): d, ppm 10.6, 20.3, 26.9,
27.0, 27.1, 27.2, 27.3, 27.4, 27.5, 28.8, 29.8, 33.0, 126.8,
129.4, 129.7, 130.1, 133.7, 135.0, 135.5, 143.2, 143.8,
148.6, 149.1, 149.5. MALDI-TOF (TCNQ): m/z found
1538.78; calcd. 1536.88. HRESI MS (THF 1:1 MeCN):
[C105H108N12+2H]2+ m/z 769.4471 found 769.4488 calcd.
Hexa(pyrrol-yl)hexaazatrinaphthalene (1b). Pre-
pared from 69 mg (0.09 mmol, 1 eq) hexa(1H-pyrrol-
2-yl)hexaazatrinaphthalene (4) and 150 mg (0.40 mmol,
4.5 eq) 4-((4-dodecylphenyl)ethynyl)benzaldehyde (6).
Yield: 137 mg (0.07 mmol, 82%) of compound 1b as
a black solid. UV-vis (CHCl3, 10-5 M): λmax, nm 291.
1H NMR (C3D2F6O plus 0.1% C2DF3O2, 500 MHz, 298
K): d, ppm 0.65 (m, 9H), 1.07 (m, 54H), 1.51 (m, 6H),
2.42 (m, 6H), 5.92 (d, 3J = 4.7 Hz, 6H), 5.99 (d, 3J = 4.7
Hz, 6H), 6.40 (s, 6H), 6.88 (d, 3J = 8.2 Hz, 6H), 7.02 (d,
3J = 8.2 Hz, 6H), 7.24 (d, 3J = 8.2 Hz, 6H), 7.30 (d, 3J =
8.2 Hz, 6H). 13C NMR (C3D2F6O plus 0.1% C2DF3O2,
176 MHz, 298 K): d, ppm 10.6, 20.3, 26.9, 27.1, 27.2,
27.3, 27.3, 27.4, 27.4, 29.0, 29.8, 33.7, 91.5, 96.4, 127.1,
129.0, 129.6, 129.7, 130.3, 131.9, 135.1, 135.2, 143.5,
144.1, 144.5, 144.8, 149.8 l. MALDI-TOF (TCNQ):
m/z found 1842.36; calcd. 1843.02. HRESI MS (THF
1:1 MeCN): [C129H120N12+2H]2+ m/z 919.4977 found
919.4958 calcd.
3
3H), 1.27 (m, 18H), 1.61 (m, 2H), 2.63 (t, J = 8.0 Hz,
2H), 7.20 (d, 3J = 8.2 Hz, 2H), 7.47 (d, 3J = 8.2 Hz, 2H),
7.67 (d, 3J = 8.2 Hz, 2H), 7.85 (d, 3J = 8.2 Hz, 2H), 10.00
(s, 1H). 13C NMR (CD2Cl2, 75 MHz, 298 K): d, ppm
14.3, 23.1, 29.6, 29.7, 29.8, 29.9, 30.0, 30.1, 31.6, 32.3,
36.2, 88.3, 93.9, 119.9, 129.0, 129.8, 130.0, 132.0, 132.3,
135.8, 144.9, 191.6.
Preparation of 4-((3,4,5-tris(decyloxy)phenyl)eth-
ynyl)benzaldehyde (9). 382 mg (0.67 mmol, 0.98 eq)
1,2,3-tris(decyloxy)-5-ethynylbenzene (17), 126 mg
(0.68 mmol, 1 eq) 4-bromobenzaldehyde (11), 60 mg
(51 µmol, 10%mol) Pd(PPh3)4 and 30 mg (158 µmol,
20%mol) CuI were dissolved in 5 mL anhydrous THF
and 20 mL diisopropylamine. The reaction mixture was
heated to 60 °C and stirred for 2 h at this temperature. The
reaction mixture was filtered over a frit and the solvent
removed in vacuo. The crude product was purified by
column chromatography using hexane:EtOAc (6:1) as
eluent, affording 355 mg (77%, 0.53 mmol) of compound
9 as a colorless liquid. 1H NMR (CD2Cl2, 300 MHz, 298
K): d, ppm 0.88 (t, 3J = 6.6 Hz, 9H), 1.29 (m, 42H), 1.79
Hexa(pyrrol-yl)hexaazatrinaphthalene (2a). Pre-
pared from 100 mg (0.13 mmol, 1 eq) hexa(1H-pyrrol-
2-yl)hexaazatrinaphthalene (4) and 191 mg (0.58 mmol,
4.5 eq) 4-(2-hexyldecyl)benzaldehyde (7). Yield: 117
mg (0.06 mmol, 52%) of compound 2a as a black
3
(m, 6H), 3.93 (dt, J = 6.5 Hz, 6H), 6.77 (s, 2H), 7.66
(d, 3J = 8.3 Hz, 2H), 7.85 (d, 3J = 8.3 Hz, 2H), 10.00 (s,
1H). 13C NMR (CD2Cl2, 75 MHz, 298 K): d, ppm 14.3,
23.1, 26.5, 29.7, 29.8, 30.0, 30.1, 30.1, 30.2, 30.7, 32.3,
32.4, 69.5, 73.9, 89.6, 94.2, 110.5, 117.1, 129.8, 129.9,
132.3, 135.9, 136.0, 153.5, 191.6. HRESI MS (THF 1:1
MeCN): [C45H70O4+Na]+ m/z 697.5192 found 697.5172
calcd.
1
solid. UV-vis (CHCl3, 10-5 M): λmax, nm 344. H NMR
(C3D2F6O plus 0.1% C2DF3O2, 700 MHz, 298 K): d, ppm
0.81 (m, 18H), 1.22 (m, 72H), 1.63 (m, 3H), 2.58 (d,
3J = 6.6 Hz, 6H), 6.18 (d, 3J = 4.5 Hz, 6H), 6.23 (d, 3J =
4.5 Hz, 6H), 6.70 (s, 6H), 7.01 (d, 3J = 7.7 Hz, 6H), 7.20
3
General procedure for the preparation of triangu-
lar hexa(pyrrol-yl)hexaazatrinaphthalene derivatives
1a–3b. Hexa(1H-pyrrol-2-yl)hexaazatrinaphthalene (4)
and the corresponding aldehydes 5–9 (4.5 eq) were
suspended in 4 mL DCM and 2 mL THF. To this solution
0.5 mL TFA were added and the reaction mixture was
degassed. The compounds were reacted under microwave
irradiation (3 × 6 h, 85 °C, 50 W). The reaction mixture
was concentrated in vacuo and the crude product was
precipitated from MeOH. The solid was filtered off and
purified by Soxhlet extraction with acetone affording the
corresponding trinuclear compound 1a–3b.
Hexa(pyrrol-yl)hexaazatrinaphthalene (1a). Pre-
pared from 119 mg (0.15 mmol, 1 eq) hexa(1H-pyrrol-
2-yl)hexaazatrinaphthalene (4) and 190 mg (0.70 mmol,
4.5 eq) 1-dodecyl-4-ethynylbenzene (5). Yield: 75 mg
(0.05 mmol, 32%) of compound 1a as a black solid.
(d, J = 7.7 Hz, 6H). MALDI-TOF (TCNQ): m/z found
1707.27; calcd. 1705.07. HRESI MS (THF 1:1 MeCN):
[C117H132N12+2H]2+ m/z 853.5408 found 853.5427 calcd.
Hexa(pyrrol-yl)hexaazatrinaphthalene (3a). Pre-
pared from 100 mg (0.13 mmol, 1 eq) hexa(1H-pyrrol-
2-yl)hexaazatrinaphthalene (4) and 383 mg (0.56 mmol,
4.5 eq) 3,4,5-tris(dodecyloxy)benzaldehyde (8). Yield:
250 mg (0.09 mmol, 71%) of compound 3a as a black
1
solid. UV-vis (CHCl3, 10-5 M): λmax, nm 364. H NMR
(C3D2F6O plus 0.1% C2DF3O2, 500 MHz, 298 K): d, ppm
0.84 (t, 27H, 2J = 6.8 Hz), 1.24 (m, 144H), 1.43 (m, 18H),
2
1.75 (m, 18H), 3.89 (t, 12H, J = 6.1 Hz), 4.12 (t, 6H,
2J = 6.8 Hz), 6.12 (d, 6H, 3J = 4.7 Hz), 6.18 (d, 6H, 3J = 4.7
Hz), 6.37 (s, 6H), 6.59 (s, 6H). 13C NMR (C3D2F6O plus
0.1% C2DF3O2, 176 MHz, 298 K): d, ppm 10.7, 20.4,
23.8, 23.9, 26.9, 27.1, 27.3, 27.4, 27.6, 27.9, 29.9, 74.0,
107.7, 128.9, 130.3, 133.8, 135.0, 135.1, 138.7, 143.6,
Copyright © 2012 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2012; 16: 567–575