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112.80, 119.92, 133.46, 133.78, 134.65, 135.76, 158.89 ppm. UV/Vis:
labs (THF) (e, mmÀ1 cmÀ1): 422 (595.1), 519 (23.9), 556 (14.9), 594
(8.3), 651 (10.8). HRMS (MALDI-TOF): Calcd for C52H46N4O4:
m/z 790.3519 ([M]+). Found: m/z 791.3522 ([M]+).
purple solid (0.2 g, 93%). H NMR (500 MHz, CDCl3): d=1.62 (t, J=
6.8 Hz, 12H), 4.34 (m, 8H), 7.27 (s, 8H), 8.11 (d, J=7.3 Hz, 8H), 8.97
(s, 8H) ppm. 13C NMR (125 MHz, CDCl3): d=15.25, 63.87, 112.67,
132.02, 135.55, 150.62, 158.73 ppm. UV/Vis: labs (THF) (e,
mmÀ1 cmÀ1): 424 (497.1), 551 (23.4), 591 (8.1). HRMS (MALDI-TOF):
Calcd for C52H44N4O4Zn: m/z 854.3102 ([M]+). Found: m/z 854.3105
([M]+).
Tetra(4-hexyloxyphenyl)porphyrin (5b): Obtained from 3b (2.0 g,
9.7 mmol) and pyrrole (0.7 mL, 9.7 mmol), by following the above
described procedure, as a purple solid (0.4 g, 18%). 1H NMR
(500 MHz, CDCl3): d=À2.73 (s, 2H), 1.00 (t, J=7.0 Hz, 12H), 1.48
(m, 16H), 1.64 (m, 8H), 1.99 (m, 8H), 4.25 (t, J=6.5 Hz, 8H), 7.26 (d,
J=8.1 Hz, 8H), 8.11 (d, J=8.4 Hz, 8H), 8.87 (s, 8H) ppm. 13C NMR
(75 MHz, CDCl3): d=14.27, 22.86, 26.08, 29.51, 29.64, 29.81, 29.85,
31.39, 31.89, 32.08, 68.45, 112.84, 119.95, 131.16, 134.60, 135.74,
159.10 ppm. UV/Vis: labs (THF) (e, mmÀ1 cmÀ1): 422 (507.6), 519
(15.7), 556 (14.4), 594 (11.9), 651 (12.6). HRMS (MALDI-TOF): Calcd
for C68H78N4O4: m/z 1015.3713 ([M]+). Found: m/z 1015.3719 ([M]+).
[Tetra(4-hexyloxyphenyl)porphyrinato]zinc(II) (ZnTHPP; 7b): Ob-
tained from 5b (0.3 g, 0.3 mmol) and Zn(CH3COO)2·2H2O (0.7 g,
3.2 mmol), by following the above described procedure, as a
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purple solid (0.3 g, 92%). H NMR (500 MHz, CDCl3): d=0.981–1.009
(m, 12H), 1.49 (m, 16H), 1.64 (m, 8H), 1.99 (p, J=14.8 Hz, 8H), 4.25
(t, J=6.5 Hz, 8H), 7.27 (d, J=8.7 Hz, 8H), 8.11 (d, J=8.6 Hz, 8H),
8.98 (s, 8H) ppm. 13C NMR (125 MHz, CDCl3): d=14.27, 22.86, 26.09,
29.66, 31.89, 68.48, 112.72, 120.98, 132.03, 135.21, 135.54, 150.65,
158.95 ppm. UV/Vis: labs (THF) (e, mmÀ1 cmÀ1): 424 (482.4), 551
(16.9), 591 (6.2). HRMS (MALDI-TOF): Calcd for C68H76N4O4Zn:
m/z 1078.7354 ([M]+). Found: m/z 1078.7359 ([M]+).
Tetra(4-dodecyloxyphenyl)porphyrin (5c): Obtained from 3c
(1.5 g, 5.2 mmol) and pyrrole (0.4 mL, 5.2 mmol), by following the
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above described procedure, as a purple solid (0.5 g, 30%). H NMR
(500 MHz, CDCl3): d=À2.75 (s, 2H), 0.90 (t, J=13.2 Hz, 12H), 1.37
(m, 64H), 1.62 (m, 8H), 1.97 (m, 8H), 4.25 (t, J=6.5 Hz, 8H), 7.27 (d,
J=7.8 Hz, 8H), 8.11 (d, J=8.5 Hz, 8H), 8.87 (s, 8H) ppm. 13C NMR
(75 MHz, CDCl3): d=14.31, 22.87, 26.39, 29.55, 29.67, 29.70, 29.83,
29.84, 29.89, 32.11, 68.46, 112.82, 119.95, 130.59, 130.86, 130.94,
131.01, 131.23, 134.58, 135.74, 159.08 ppm. UV/Vis: labs (THF) (e,
mmÀ1 cmÀ1): 422 (496.6), 519 (17.9), 556 (13.3), 594 (5.5), 650 (6.5).
HRMS (MALDI-TOF): Calcd for C92H127N4O4: m/z 1353.0172
([M+H]+). Found: m/z 1353.0181 ([M+H]+).
[Tetra(4-dodecyloxyphenyl)porphyrinato]zinc(II) (ZnTDPP; 7c):
Obtained from 5c (0.3 g, 0.2 mmol) and Zn(CH3COO)2·2H2O (0.5 g,
2.3 mmol), by following the above described procedure, as a
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purple solid (0.3 g, 94%). H NMR (500 MHz, CDCl3): d=0.90 (t, J=
6.1 Hz, 12H), 1.31 (m, 64H), 1.62 (m, 8H), 1.99 (m, 8H), 4.25 (t, J=
6.4 Hz, 8H), 7.27 (d, J=6.7 Hz, 8H), 8.11 (d, J=8.4 Hz, 8H), 8.98 (s,
8H) ppm. 13C NMR (75 MHz, CDCl3): d 14.31, 22.87, 26.40, 29.54,
29.69, 29.84, 32.09, 68.44, 112.67, 120.96, 132.02, 135.16, 135.53,
150.61, 159.05 ppm. UV/vis: labs (THF) (e, mmÀ1 cmÀ1): 424 (496.9),
551 (14.8), 591 (5.4). HRMS (MALDI-TOF): Calcd for C92H124N4O4Zn:
m/z 1415.3734 ([M]+). Found: m/z 1415.3738 ([M]+).
Tetra(3,4-diethoxyphenyl)porphyrin (6a): Obtained from 4a
(0.7 g, 3.6 mmol) and pyrrole (0.3 mL, 3.6 mmol), by following the
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above described procedure, as a purple solid (0.2 g, 19%). H NMR
[Tetra(3,4-diethoxyphenyl)porphyrinato]zinc(II) (ZnTbEPP; 8a):
Obtained from 6a (0.2 g, 0.2 mmol) and Zn(CH3COO)2·2H2O (0.4 g,
1.8 mmol), by following the above described procedure, as a
(300 MHz, CDCl3): d=À2.75 (s, 2H), 1.52 (t, J=6.9 Hz, 12H), 1.67 (t,
J=6.9 Hz, 12H), 4.23 (q, J=4.2 Hz, 8H), 4.39 (q, J=4.4 Hz, 8H),
7.25 (d, J=2.5 Hz, 4H), 7.71 (d, J=7.2 Hz, 4H), 7.79 (s, 4H), 8.91 (s,
8H) ppm. HRMS (MALDI-TOF): Calcd for C60H62N4O8: m/z 967.1563
([M]+). Found: m/z 967.1569 ([M]+).
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purple solid (0.2 g, 94%). H NMR (500 MHz, CDCl3): d=1.50 (t, J=
7.0 Hz, 12H), 1.67 (t, J=6.9 Hz, 12h), 4.21 (q, J=7.0 Hz, 8H), 4.40 (t,
J=6.9 Hz, 8H), 7.24 (d, J=8.3 Hz, 4H), 7.72 (d, J=8.3 Hz, 4H), 7.78
(s, 4H), 9.01 (s, 8H) ppm. 13C NMR (75 MHz, CDCl3): d=15.05, 15.24,
64.72, 64.85, 111.33, 120.22, 121.08, 127.43, 132.06, 135.52, 146.64,
148.48, 150.58 ppm. UV/Vis: labs (THF) (e, mmÀ1 cmÀ1): 426 (442.9),
550 (18.1), 590 (5.8). HRMS (MALDI-TOF): Calcd for C60H61N4O8Zn:
m/z 1031.5283 ([M+H]+). Found: m/z 1031.5289 ([M+H]+).
Tetra[3,4-di(hexyloxy)phenyl]porphyrin (6b): Obtained from 4b
(1.0 g, 3.3 mmol) and pyrrole (0.2 mL, 3.3 mmol), by following the
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above described procedure, as a purple solid (0.2 g, 18%). H NMR
(300 MHz, CDCl3): d=À2.75 (s, 2H), 0.87 (m, 12H), 1.01 (m, 12H),
1.33 (m, 16H), 1.48 (m, 24H), 1.6 (m, 8H), 1.90 (m, 8H), 2.04 (m,
8H), 4.13 (t, J=6.1 Hz, 8H), 4.30 (t, J=6.1 Hz, 8H), 7.23 (m, 4H),
7.71 (d, J=7.2 Hz, 4H), 7.79 (s, 4H), 8.92 (s, 8H) ppm. HRMS
(MALDI-TOF): Calcd for C92H126N4O8: m/z 1416.0068 ([M]+). Found:
m/z 1416.0070 ([M]+).
{Tetra[3,4-di(hexyloxy)phenyl]porphyrinato}zinc(II)
(ZnTbHPP;
8b): Obtained from 6b (0.2 g, 0.1 mmol) and Zn(CH3COO)2·2H2O
(0.3 g, 1.4 mmol), by following the above described procedure, as a
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purple solid (0.2 g, 96%). H NMR (500 MHz, CDCl3): d=0.86 (t, J=
6.6 Hz, 12H), 1.00 (t, J=7.0 Hz, 12H), 1.33 (m, 16H), 1.47 (m, 24H),
1.66 (m, 8H), 1.88 (m, 8H), 2.03 (m, 8H), 4.10 (t, J=6.8 Hz, 8H),
4.29 (t, J=6.6 Hz, 8H), 7.23 (d, J=7.9 Hz, 4H), 7.71 (d, J=7.9 Hz,
4H), 7.77 (br s, 4H), 9.02 (s, 8H) ppm. 13C NMR (75 MHz, CDCl3): d=
14.14, 14.27, 14.81, 22.73, 22.87, 25.87, 26.06, 29.47, 29.66, 29.85,
30.30, 31.46, 31.75, 31.91, 38.29, 69.50, 69.57, 111.72, 117.92,
120.64, 121.12, 127.49, 132.07, 135.57, 147.06, 148.23, 148.88,
150.59 ppm. UV/Vis: labs (THF) (e, mmÀ1 cmÀ1): 426 (553.4), 550
(21.3), 590 (7.0). HRMS (MALDI-TOF): Calcd for C92H124N4O8Zn:
m/z 1479.3710 ([M]+). Found: m/z 147.3716 ([M]+).
Tetra[3,4-bis(dodecyloxy)phenyl]porphyrin (6c): Obtained from
4c (1.5 g, 3.2 mmol) and pyrrole (0.2 mL, 3.2 mmol), by following
the above described procedure, as a purple solid (0.4 g, 24%).
1H NMR (300 MHz, CDCl3): d=À2.76 (s, 2H), 0.86 (m, 24H), 1.28 (m,
120H), 1.46 (m, 16H), 1.64 (m, 8H), 1.88 (m, 8H), 2.03 (m, 8H), 4.12
(t, J=6.4 Hz, 8H), 4.30 (t, J=6.4 Hz, 8H), 7.23 (m, 4H), 7.71 (d, J=
7.4 Hz, 4H), 7.78 (s, 4H), 8.91 (s, 8H) ppm. HRMS (MALDI-TOF):
Calcd for C140H223N4O8: m/z 2090.2906 ([M+H]+). Found: m/z
2090.2914 ([M+H]+).
Synthesis
of
[tetra(4-ethoxyphenyl)porphyrinato]zinc(II)
{Tetra[3,4-bis(dodecyloxy)phenyl]porphyrinato}zinc(II)
(ZnTEPP; 7a): A MeOH (3 mL) solution of Zn(CH3COO)2·2H2O
(0.5 g, 2.3 mmol) was added to a CH2Cl2 (20 mL) solution of (5a)
(0.2 g, 0.3 mmol) and the mixture was stirred at room temperature
overnight. After the volatiles had been distilled off under vacuum,
the residue was purified by column chromatography (SiO2;
hexane/CH2Cl2 (6:4 v/v)) to collect the desirable product as a
(ZnTbDPP; 8c): Obtained from 6c (0.3 g, 0.1 mmol) and
Zn(CH3COO)2·2H2O (0.4 g, 1.8 mmol), by following the above de-
scribed procedure, as
(500 MHz, CDCl3): d=0.89 (m, 24H), 1.27 (m, 120H), 1.46 (m, 16H),
1.66 (m, 8H), 1.89 (m, 8H), 2.04 (m, 8H), 4.10 (t, J=6.7 Hz, 8H),
4.30 (t, J=6.4 Hz, 8H), 7.23 (d, J=8.1 Hz, 4H), 7.72 (d, J=7.9 Hz,
a
purple solid (0.3 g, 95%). 1H NMR
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ChemPlusChem 2017, 82, 1 – 13
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