Building Blocks for the Construction of Multiporphyrin Arrays
Compound 12: A mixture of 11 (85 mg, 0.58 mmol), CH2Cl2
(5 mL), and CF3CO2H (5 mL) was stirred at room temperature.
After 16 h, the mixture was poured into water (100 mL) and the
excess of acid neutralized by adding a saturated aqueous solution
of Na2CO3. The organic layer was then washed with H2O, dried
(Na2SO4) and the solvents evaporated. A rapid filtration through
SiO2 (hexane/CH2Cl2, 1:1) yielded 12 (74 mg, 90%). Brown-red
= 2 Hz, 2 H), 8.18 (d, J = 2 Hz, 4 H), 8.31 (d, J = 8 Hz, 2 H), 8.46
(d, J = 8 Hz, 2 H), 8.64 (s, 4 H), 8.78 (s, 4 H), 8.90 (d, J = 5 Hz,
2 H), 8.95 (d, J = 5 Hz, 2 H), 8.98 (d, J = 5 Hz, 2 H), 9.08 (d, J =
5 Hz, 2 H), 9.28 (d, J = 5 Hz, 2 H), 9.29 (d, J = 5 Hz, 2 H), 10.41 (s,
1 H) ppm. MALDI-TOF MS: 1601 (MH+, calcd. for C113H115N8O:
1601.21).
Compound 23: As described for 13, with 22 (210 mg, 0.132 mmol)
and zinc acetate dihydrate (480 mg, 2.19 mmol). Column
chromatography on SiO2 (CH2Cl2/hexane, 6:4) followed by gel per-
meation chromatography (Biorad, Biobeads SX-1, toluene) yielded
23 (228 mg, 99%). Purple glassy compound. UV/Vis (CH2Cl2):
λmax = 250, 308, 349 (sh), 418, 431, 550, 590 nm. 1H NMR
(300 MHz, CDCl3): δ = 1.56 (s, 18 H), 1.59 (s, 36 H), 1.92 (s, 12
H), 2.69 (s, 6 H), 7.35 (s, 4 H), 7.83 (t, J = 2 Hz, 1 H), 7.86 (t, J =
2 Hz, 2 H), 8.14 (d, J = 2 Hz, 2 H), 8.20 (d, J = 2 Hz, 4 H), 8.29
(d, J = 8 Hz, 2 H), 8.48 (d, J = 8 Hz, 2 H), 8.65 (s, 4 H), 8.87 (s,
4 H), 9.00 (d, J = 5 Hz, 2 H), 9.07 (d, J = 5 Hz, 2 H), 9.09 (d, J =
5 Hz, 2 H), 9.20 (d, J = 5 Hz, 2 H), 9.40 (d, J = 5 Hz, 2 H), 9.43 (d,
J = 5 Hz, 2 H), 10.38 (s, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 21.5, 21.7, 31.75, 31.8, 35.05, 35.1, 118.4, 119.8, 120.5, 120.7,
120.8, 122.6, 122.7, 127.8, 127.9, 129.6, 129.8, 131.2, 131.3, 131.8,
132.3, 132.35, 132.3, 132.5, 132.6, 132.65, 132.7, 132.8, 135.1,
135.4, 137.6, 138.9, 139.3, 141.8, 141.9, 142.3, 148.6, 148.65, 149.4,
149.5, 150.0, 150.2, 150.3, 150.4, 150.5, 150.6, 192.5 ppm. MALDI-
TOF MS: 1727 (M+, calcd. for C113H110N8OZn2: 1726.92).
glassy product. IR (CH Cl ): ν = 1751, 1701 (C=O) cm–1. UV/Vis
˜
2
2
(CH2Cl2): λmax = 257, 323 (sh), 420, 514, 548, 591, 647 nm. 1H
NMR (300 MHz, CDCl3): δ = –2.61 (br. s, 2 H), 0.86 (t, J = 7 Hz,
12 H), 1.10–1.40 (m, 72 H), 1.65 (m, 8 H), 1.80 (s, 6 H), 1.87 (s, 6
H), 2.61 (s, 3 H), 2.65 (s, 3 H), 3.81 (t, J = 6.5 Hz, 8 H), 5.30 (d,
J = 12 Hz, 2 H), 5.37 (m, 4 H), 6.01 (d, J = 12 Hz, 2 H), 6.32 (t,
J = 2 Hz, 4 H), 6.50 (d, J = 2 Hz, 4 H), 7.24 (s, 2 H), 7.31 (s, 2 H),
7.98 (t, J = 1 Hz, 1 H), 8.19 (d, J = 1 Hz, 2 H), 8.30 (d, J = 7 Hz,
2 H), 8.44 (d, J = 7 Hz, 2 H), 8.62 (d, J = 5 Hz, 1 H), 8.74 (d, J =
5 Hz, 1 H), 8.75 (s, 2 H), 8.77 (d, J = 5 Hz, 1 H), 8.79 (d, J = 5 Hz,
1 H), 8.91 (d, J = 5 Hz, 1 H), 10.40 (s, 1 H) ppm. MALDI-TOF
MS: 2594 (MH+, calcd. for C181H154N4O13: 2594.24).
C181H154N4O13 (2593.23): calcd. C 83.03, H 5.99; found C 87.74,
H 6.25.
Compound 13: A mixture of 12 (74 mg, 0.028 mmol) and zinc ace-
tate dihydrate (30 mg, 0.14 mmol) in CHCl3/MeOH, 9:1 (5 mL) was
refluxed for 2 h and the solvents evaporated. Column chromatog-
raphy on SiO2 (CH2Cl2/hexane, 5:4) yielded 13 (66 mg, 87%).
C113H110N8OZn2 (1726.92): calcd. C 78.59, H 6.42; found C 78.25,
Brown-red glassy product. IR (CH Cl ): ν = 1749, 1702 (C=O)
˜
2
2
cm–1. UV/Vis (CH2Cl2): λmax = 257, 323 (sh), 420, 550, 587 nm. 1H
NMR (300 MHz, CDCl3): δ = 0.87 (t, J = 7 Hz, 12 H), 1.10–1.40
(m, 72 H), 1.68 (m, 8 H), 1.77 (s, 6 H), 1.88 (s, 6 H), 2.65 (s, 3 H),
2.66 (s, 3 H), 3.83 (t, J = 6.5 Hz, 8 H), 5.24 (d, J = 12 Hz, 2 H),
5.35 (d, J = 12 Hz, 2 H), 5.37 (d, J = 12 Hz, 2 H), 5.83 (d, J =
12 Hz, 2 H), 6.33 (t, J = 1.5 Hz, 4 H), 6.50 (d, J = 1.5 Hz, 4 H),
7.17 (s, 2 H), 7.31 (s, 2 H), 8.00 (s, 1 H), 8.11 (s, 2 H), 8.35 (d, J =
7 Hz, 2 H), 8.53 (d, J = 5 Hz, 1 H), 8.63 (d, J = 7 Hz, 2 H), 8.80
(d, J = 5 Hz, 1 H), 8.83 (d, J = 5 Hz, 1 H), 8.86 (d, J = 5 Hz, 1
H), 8.88 (d, J = 5 Hz, 1 H), 8.90 (d, J = 5 Hz, 1 H), 8.92 (m, 2
H), 10.37 (s, 1 H) ppm. MALDI-TOF MS: 2658 (MH+, calcd. for
C181H152N4O13Zn: 2657.60). C181H152N4O13Zn (2656.60): calcd. C
81.83, H 5.77; found C 81.52, H 5.69.
H 6.66.
Compound 24: As described for 11, with 23 (39 mg, 0.022 mmol)
and pyrrole (0.022 mmol). Two successive purification steps by col-
umn chromatography on SiO2 (CH2Cl2/hexane, 4:5) followed by
gel permeation chromatography (Biorad, Biobeads SX-1, toluene)
yielded 24 (8 mg, 20%). Purple glassy compound. UV/Vis
(CH2Cl2): λmax = 248, 306, 352, 420, 439, 516, 551, 592, 648 nm.
1H NMR (300 MHz, CDCl3): δ = –2.49 (br. s, 2 H), 1.58 (s, 72 H),
1.62 (s, 144 H), 2.09 (s, 48 H), 2.81 (s, 24 H), 7.48 (s, 16 H), 7.84
(t, J = 1.5 Hz, 4 H), 7.89 (t, J = 1.5 Hz, 8 H), 8.16 (d, J = 1.5 Hz,
8 H), 8.23 (m, 16 H), 8.71 (d, J = 8 Hz, 8 H), 8.74 (d, J = 8 Hz, 8
H), 8.88 (d, J = 8 Hz, 8 H), 8.92 (d, J = 8 Hz, 8 H), 9.09 (d, J =
5 Hz, 8 H), 9.11 (d, J = 5 Hz, 16 H), 9.16 (d, J = 5 Hz, 8 H), 9.24
(d, J = 5 Hz, 8 H), 9.48 (d, J = 5 Hz, 8 H), 9.71 (s, 8 H), 9.49 (d,
J = 5 Hz, 8 H), 9.56 (d, J = 5 Hz, 8 H) ppm. MALDI-TOF MS:
7098 (M+, calcd. for C468H446N36Zn8: 7097.97).
Compound 21: As described for 11, with 20 (830 mg, 0.796 mmol), 9
(175 mg, 0.796 mmol) and 10 (421 mg, 1.59 mmol). Four successive
purification steps by column chromatography on SiO2 (CH2Cl2/
hexane, 6:4) followed by gel permeation chromatography (Biorad,
Biobeads SX-1, toluene) yielded 21 (231 mg, 17%). Purple glassy
compound. UV/Vis (CH2Cl2): λmax = 248, 306, 352, 418, 429, 515,
Compound 25: As described for 13, with 24 (7 mg, 0.001 mmol) and
zinc acetate dihydrate (3 mg, 0.014 mmol). Column chromatog-
raphy on SiO2 (CH2Cl2/hexane, 4:5) followed by gel permeation
chromatography (Biorad, Biobeads SX-1, toluene) yielded 25
1
551, 590, 647 nm. H NMR (300 MHz, CDCl3): δ = –2.38 (br. s, 2
H), 0.97 (s, 3 H), 1.54 (s, 3 H), 1.63 (s, 18 H), 1.66 (s, 36 H), 2.00
(s, 12 H), 2.74 (s, 6 H), 3.90 (d, J = 11 Hz, 2 H), 4.03 (d, J = 11 Hz,
2 H), 5.80 (s, 1 H), 7.41 (s, 4 H), 7.90 (t, J = 2 Hz, 1 H), 7.93 (t, J
= 2 Hz, 2 H), 7.99 (d, J = 8 Hz, 2 H), 8.22 (d, J = 2 Hz, 2 H), 8.27
(d, J = 2 Hz, 4 H), 8.37 (d, J = 8 Hz, 2 H), 8.73 (s, 4 H), 8.82 (d,
J = 5 Hz, 2 H), 8.93 (d, J = 5 Hz, 2 H), 8.98 (d, J = 5 Hz, 2 H),
9.15 (d, J = 5 Hz, 2 H), 9.18 (d, J = 5 Hz, 2 H), 9.28 (d, J = 5 Hz,
2 H), 9.38 (d, J = 5 Hz, 2 H), 9.49 (d, J = 5 Hz, 2 H) ppm.
(5.5 mg, 78%). Purple glassy compound. UV/Vis (CH2Cl2): λmax
=
250, 308, 349 (sh), 420, 439, 551, 592 nm. 1H NMR (300 MHz,
CDCl3): δ = 1.57 (s, 72 H), 1.61 (s, 144 H), 2.09 (s, 48 H), 2.81 (s,
24 H), 7.48 (s, 16 H), 7.84 (t, J = 1.5 Hz, 4 H), 7.83 (t, J = 1.5 Hz,
8 H), 8.16 (d, J = 1.5 Hz, 8 H), 8.27 (d, J = 1.5 Hz, 16 H), 8.71 (d,
J = 8 Hz, 8 H), 8.74 (d, J = 8 Hz, 8 H), 8.88 (d, J = 8 Hz, 8 H),
8.92 (d, J = 8 Hz, 8 H), 9.09 (d, J = 5 Hz, 8 H), 9.11 (m, 24 H),
9.17 (d, J = 5 Hz, 8 H), 9.24 (d, J = 5 Hz, 8 H), 9.49 (m, 16 H),
9.59 (d, J = 5 Hz, 8 H), 9.82 (s, 8 H) ppm. MALDI-TOF MS:
7161 (M+, calcd. for C468H444N36Zn9: 7161.33). C468H444N36Zn9
(7161.33): calcd. C 78.49, H 6.25; found C 78.11, H 6.56.
Compound 22: As described for 12, with 21 (230 mg, 0.132 mmol).
Column chromatography on SiO2 (CH2Cl2/hexane, 6:4) followed by
gel permeation chromatography (Biorad, Biobeads SX-1, toluene)
yielded 22 (211 mg, 93%). Purple glassy compound. UV/Vis
(CH2Cl2): λmax = 250, 306, 352, 418, 430, 515, 550, 590, 648 nm.
Compound 26: As described for 11, with 13 (66 mg, 0.025 mmol)
and pyrrole (0.025 mmol). Two successive purification steps by col-
1H NMR (300 MHz, CDCl3): δ = –2.53 (br. s, 2 H), –2.45 (br. s, 2 umn chromatography on SiO2 (CH2Cl2/hexane, 1:1) followed by
H), 1.55 (s, 18 H), 1.58 (s, 36 H), 1.93 (s, 12 H), 2.68 (s, 6 H), 7.35
gel permeation chromatography (Biorad, Biobeads SX-1, toluene)
(s, 4 H), 7.82 (t, J = 2 Hz, 1 H), 7.85 (t, J = 2 Hz, 2 H), 8.12 (d, J
yielded 26 (38 mg, 57%). Brown-red glassy compound. IR (KBr):
Eur. J. Org. Chem. 2009, 3715–3725
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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