486
J. LUDWIG ET AL.
3
3
mixture was diluted with dichloromethane (150 mL) and
deionized water (150 mL) and neutralized. The layers
were separated and the aqueous layer was extracted with
dichloromethane (3 × 100 mL). The combined organic
layer was dried over magnesium sulfate and the solvent
was removed in vacuo. The crude product was absorbed
on silica and column chromatography on silica (SNAP
H-10), 7.08 (1H, d, J = 7.96 Hz, H-12), 6.76 (1H, d, J =
3 19
5.76 Hz, H-5), 6.64 (1H, t, J = 7.95 Hz, H-11). F NMR
(471 MHz, acetone-d ; 300 K): d , ppm -139.55– -140.16
(6F, ortho-F), -155.71– -155.75 (3F, para-F), -164.34–
-164.88 (6F, meta-F). MALDI-TOF-MS (Cl-CCA): m/z
6
F
+
1082 (calcd. for [M + H] 1082).
Preparation of Ni-porphyrin 15. Metal-free porphyrin
14 (46.0 mg, 42.6 mmol) and nickel(II) acetylacetonate
(87.5 mg, 699 mmol) were dissolved in toluene (40 mL)
and refluxed for 4 d. The solvent was removed
in vacuo and the crude product was purified by column
Ultra 340 g, DCM/MeOH: 99:1 à 9:1, R (DCM/
f
MeOH, 85:15) = 0.56) was performed. The product was
obtained as an orange solid. Yield: 1.93 g (82%), mp
2
7
1
11°C (decomposition). Anal. Calcd. for C H N O : C,
1
8
13
3
2
1.28; H, 4.32; N, 13.85%. Found: C, 70.31; H, 4.37; N,
chromatography on silica (chloroform, R = 0.15). The
product was obtained as a red solid.Yield: 28.5 mg (52%),
f
1
3.67%. H NMR (500 MHz, DMSO-d , TFA-d ; 298 K,
6
1
4
1
Me Si): d , ppm 9.98 (1H, s, COH), 8.87 (1H, d, J = 1.15
mp > 300°C. H NMR (500 MHz, acetone-d , TFA-d ;
4
H
6
1
3
4
Hz, H-2), 8.63 (1H, dd, J = 6.85 Hz, J = 1.15 Hz, H-6),
298 K, Me Si): d , ppm 9.15 (4H, s, b-pyrrolic-H-3/4),
3
4
H
3
4
8
.12 (1H, dt, J = 7.75 Hz, J = 1.62 Hz, H-12), 8.07 (1H,
9.06 (2H, d, J = 5.00 Hz, b-pyrrolic-H-2), 9.00 (2H, d,
4
3
4
3
4
t, J = 1.57 Hz, H-8), 8.01 (1H, dd, J = 7.66 Hz, J =
1
H-16), 7.79 (1H, t, J = 7.62 Hz, H-11), 7.75 (1H, dt, J =
7
7
J = 5.00 Hz, b-pyrrolic-H-1), 8.93 (1H, d, J = 1.25 Hz,
3
4
3
4
.14 Hz, H-15), 7.82 (1H, td, J = 7.50 Hz, J = 1.41 Hz,
H-2), 8.81 (1H, dd, J = 6.96 Hz, J = 1.25 Hz, H-6),
3 4
3
3
8.38 (1H, dd, J = 7.66 Hz, J = 1.30 Hz, H-15), 8.03
3 4
4
.55 Hz, J = 1.37 Hz, H-10), 7.69–7.65 (1H, m, H-17),
(1H, td, J = 7.71 Hz, J = 1.32 Hz, H-17), 7.92 (1H,
3 4
3
4
.62 (1H, dd, J = 7.68 Hz, J = 0.78 Hz, H-18), 7.51 (1H,
td, J = 7.70 Hz, J = 1.16 Hz, H-16), 7.90 (1H, dd,
3 4 4
3
13
d, J = 6.85 Hz, H-5). C NMR (125 MHz, DMSO-d6,
TFA-d ; 298 K, Me Si): d , ppm 191.4 (1C, COH), 168.1
J = 7.71 Hz, J = 1.14 Hz, H-18), 7.77 (1H, t, J = 1.75
3
Hz, H-8), 7.58 (1H, d, J = 6.96 Hz, H-5), 7.21 (1H,
1
4
C
3
4
4
(
1C, C-4), 151.5 (1C, C-7), 143.5 (1C, C-13), 142.7 (1C,
ddd, J = 7.98 Hz, J = 1.75 Hz, J = 1.02 Hz, H-10),
3 4 4
C-6), 138.9 (1C, C-9), 137.5 (1C, C-3), 133.9 (1C, C-10),
7.15 (1H, ddd, J = 7.98 Hz, J = 1.99 Hz, J = 1.02 Hz,
3
19
1
1
1
1
1
1
1
6
33.9 (1C, C-16), 133.2 (1C, C-14), 132.1 (1C, C-2),
30.8 (1C, C-18), 129.6 (1C, C-11), 128.4 (1C, C-17),
27.9 (1C, C-15), 123.7 (1C, C-8), 123.4 (1C, C-12),
16.1 (1C, C-5). FT-IR (ATR) ν, cm : 3027, 2597,
993, 1685, 1633, 1598, 1558, 1520, 1505, 1455, 1411,
372, 1291, 1274, 1244, 1199, 1184, 1174, 1154, 1102,
031, 1000, 943, 900, 843, 815, 771, 743, 726, 663, 647,
19, 600, 572, 540, 506. UV-vis (acetonitrile): lmax, nm
H-12), 6.74 (1H, t, J = 7.98 Hz, H-11). F NMR (471
MHz, acetone-d , TFA-d ; 298 K): d , ppm -138.67–
6
1
F
-139.63 (6F, ortho-F), -154.42–-154.66 (3F, para-F),
-163.14–-163.68 (6F, meta-F). FT-IR (ATR) ν, cm :
2923, 2853, 2361, 1343, 1610, 1518, 1489, 1344, 1159,
1052, 987, 955, 937, 799, 726, 709, 695, 660,585. UV-vis
(acetonitrile): lmax, nm (log e): 406 (5.20), 524 (4.08), 556
(3.92). MALDI-TOF-MS (Cl-CCA): m/z 1138 (calcd. for
-
1
-1
+
(
log e): 232 (4.35), 342 (4.11). HR-EI-MS (70 eV): m/z
[M + H] 1138). HR-ESI-MS: m/z 1136.07898 (calcd. for
[M – H]- 1136.07705).
+
3
03.10050 (calcd. for [M] 303.10078).
Preparation of metal-free porphyrin 14. 3-(3-(2-
Formylphenyl)phenylazo)-4-hydroxypyridine (365 mg,
.18 mmol, 11), pentafluorobenzaldehyde (230 mg,
.18 mmol, 13) and boron trifluoride diethyl etherate
341 mg, 2.40 mmol) were dissolved under an
atmosphere of nitrogen in chloroform (250 mL). meso-
Pentafluorophenyldipyrromethane (733 mg, 2.35 mmol,
2) was dissolved in chloroform (20 mL) and added
Preparation of Ni-porphyrin-G[2.1] 16. In flame-
dried glassware under nitrogen atmosphere, sodium
hydride (42.2 mg, 1.05 mmol) and G[2.1]-H dendron
(147 mg, 211 µmol) were suspended/dissolved in dry
tetrahydrofuran (THF, 40 mL) and stirred for 30 min
at ambient temperature. Ni-porphyrin 15 (40.0 mg,
35.1 mmol) was added and stirred for 7 d at ambient
temperature. The mixture was diluted with deionized
1
1
(
1
over a period of 30 min. After 5 h of stirring at ambient
temperature, p-chloranil (606 mg, 2.85 mmol) was added
and refluxed for 12 h. The cold mixture was filtered
through Celite , the solvent was removed in vacuo and the
crude product was purified by column chromatography
water, dichloromethane and a saturated solution
of sodium chloride (each 50 mL). The layers were
separated and the aqueous layer was extracted with
dichloromethane (2 × 25 mL). The combined organic
layer was dried over magnesium sulfate and the solvent
was removed in vacuo. The crude product was purified
by column chromatography on silica (toluene/diethyl
®
on silica (cyclohexane/ethyl acetate, 6:1, R = 0.13).
f
The product was obtained as a red solid. Yield: 51.7 mg
1
(
4%). H NMR (500 MHz, acetone-d ; 300 K, Me Si):
ether/ethanol, 45:45:10, R = 0.24) to obtain a red oil.
6
4
f
1
dH, ppm 9.25 (4H, s, b-pyrrolic-H-3/4), 9.18 (2H, s,
b-pyrrolic-H-2), 9.11 (2H, s, b-pyrrolic-H-1), 8.41 (1H,
Yield: 65.0 mg (58%). H NMR (500 MHz, acetone-d ,
6
TFA-d ; 298 K, Me Si): d , ppm 9.08–8.93 (8H, m,
1
4
H
3
3
s, H-2), 8.36 (1H, d, J = 7.67 Hz, H-15), 8.24 (1H, d, J =
b-pyrrolic-H-1/2/3/4), 8.92 (1H, s, H-2) 8.78 (1H, d,
3
3
5
.76 Hz, H-6), 8.07 (1H, t, J = 7.70 Hz, H-17), 8.01 (1H,
J = 6.11 Hz, H-6), 8.42–8.31 (1H, m, br, H-15), 7.99
3
3
3
3
d, J = 7.87 Hz, H-18), 7.92 (1H, t, J = 7.49 Hz, H-16),
(1H, t, J = 7.81 Hz, H-17), 7.90 (1H, d, J = 6.65 Hz,
H-18), 7.97 (1H, t, J = 6.40 Hz, H-16), 7.73 (1H, s,
4
3
3
7
.86 (1H, t, J = 1.70 Hz, H-8), 7.21 (1H, d, J = 7.88 Hz,
Copyright © 2020 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2020; 24: 486–488