Water-Soluble Dendronized Perylenecarboxdiimides
31.98 (1 C, CH2), 37.10 (1 C, CH2), 41.36 (1 C, CH2), 57.23 (1 C, C, quat. C-N), 80.42 (18 C, quat. C tBu), 123.18, 126.35, 129.29,
quat. C-N), 80.62 (3 C, quat. C tBu), 172.49 (1 C, CONH), 172.89 131.47, 134.60 (20 C, Ar-C), 163.42 (4 C, CON), 172.70 (18 C,
(3 C, COOR) ppm. IR: ν = 3304, 2980, 2937, 2872, 1725, 1644,
COOR), 172.91 (6 C, CONH), 173.13 (2 C, CONH) ppm. IR: ν =
˜
˜
1548, 1459, 1420, 1393, 1366, 1316, 1251, 1216, 1146, 1100, 1038,
950, 849, 760, 679 cm–1. C28H52N2O7 (530)ϫ0.17 CHCl3: calcd. C
61.74, H 9.66, N 5.09; found C 61.66, H 9.58, N 5.11.
2976, 1729, 1656, 1594, 1544, 1455, 1393, 1366, 1316, 1254, 1216,
1150, 1100, 1031, 957, 849, 811 cm–1. UV/Vis (CHCl3): λmax
=
458 nm, 489, 526; fluorescence: λmax
= 533 nm, 576, 621.
C188H294N10O48 (3461)ϫ1 CHCl3: C 63.38, H 8.30, N 3.91; found
C 63.63, H 8.60, N 3.73.
Compound 8b: Yield 5.677 g (86.9%).1H NMR (300 MHz, CDCl3,
25 °C): δ = 1.41 (s, 81 H, CH3), 1.55 (m, 6 H, CH2), 1.94 (m, 24
H, CH2), 2.16 (m, 26 H, CH2), 3.19 (m, 2 H, 18), 5.07 (s, 2 H, Ar-
CH2-O), 5.26 (m, 1 H, NH), 6.09 (br. s, 3 H, NH), 7.31 (m, 5 H,
Ar-CH), 7.68 (br. s, 1 H, NH) ppm. 13C NMR (75 MHz, CDCl3,
25 °C): δ = 24.30, 25.24, 26.17 (3 C, CH2), 28.04 (27 C, CH3), 29.49,
29.76 (18 C, CH2), 31.69 (3 C, CH2), 31.90 (3 C, CH2), 36.93 (1 C,
CH2-CO), 40.81 (1 C, CH2-NH), 57.46 (3 C, quat. C-N), 57.63 (1
C, quat. C-N), 66.43 (1 C, Ar-CH2-O), 80.57 (9 C, quat. C tBu),
127.91, 128.04, 128.40 (5 C, Ar-CH), 136.76 (1 C, Ar-C), 156.47
(1 C, NHCOOBz), 172.67 (9 C, COOR), 172.88 (3 C, CONH),
N,NЈ-Substituted Perylene-3,4:9,10-tetracarboxdiimide 1a: Yield
1
0.386 g (99.04%). H NMR (300 MHz, CDCl3:TFA, 3:1, 25 °C): δ
= 1.55 (m, 4 H, CH2), 1.82 (m, 8 H, CH2), 2.20 (m, 12 H, CH2),
3
2.43 (m, 4 H, CH2), 2.52 (m, 12 H, CH2), 4.30 (t, J = 7.35 Hz, 4
H, CH2-N), 6.70 (br. s, 2 H, NH) 8.06 (s, 3 H, COOH), 8.74 (m, 8
H, Ar-CH) ppm. 13C NMR (100 MHz, CDCl3/TFA, 1:1, 25 °C): δ
= 25.29, 26.12, 26.88 (6 C, CH2), 28.23 (6 C, CH2), 29.06 (6 C,
CH2), 36.17 (2 C, CH2), 41.86 (2 C, CH2-N), 59.35 (2 C, quat. C-
N), 122.28, 124.39, 126.42, 129.34, 133.06, 135.82 (20 C, Ar-C),
167.58 (4 C, CON), 178.26 (2 C, CONH), 180.41 (6 C, COOH)
173.31 (1 C, CONH) ppm. IR: ν = 3308, 2976, 2934, 1725, 1652,
˜
ppm. IR: ν = 2930, 2856, 2706–2559, 1691, 1644, 1594, 1575, 1544,
˜
1536, 1455, 1420, 1393, 1366, 1316, 1251, 1216, 1150, 1104, 1031,
953, 849, 757, 699 cm–1. C90H151N5O24 (1688): calcd. C 64.07, H
9.02, N 4.15; found C 63.83, H 8.92, N 4.25.
1444, 1420, 1401, 1382, 1343, 1289, 1254, 1181, 1131, 811, 754,
721, 668 cm–1. UV/Vis (phosphate buffer pH 7.2): λmax = 501 nm,
537; fluorescence: λmax = 549 nm, 589. C56H60N4O18 (1078)ϫ2
HCOOH: C 59.58, H 5.52, N 4.79; found C 59.35, H 5.69, N 4.97.
Compound 9b: Yield 0.245 g (96.04%). 1H NMR (300 MHz,
CDCl3, 25 °C): δ = 1.42 (s, 81 H, CH3), 1.67, 1.85 (m, 6 H, CH2),
N,NЈ-Substituted Perylene-3,4:9,10-tetracarboxdiimide 1b: Yield
0.082 g (98.7%). 1H NMR (400 MHz, CDCl3/TFA, 1:1, 25 °C): δ
= 1.54, 1.76, 1.83 (m, 12 H, CH2), 2.19 (m, 48 H, CH2), 2.32 (m,
4 H, CH2), 2.48 (m, 48 H, CH2), 4.30 (m, 4 H, CH2), 7.10 (br. s,
6 H, NH), 7.17 (2 H, NH), 8.84 (m, 8 H, Ar-CH) ppm. 13C NMR
(100 MHz, CDCl3/TFA, 1:1, 25 °C): δ = 25.91, 26. 57, 27.26 (3 C,
CH2), 28.32 (18 C, CH2), 29.14 (18 C, CH2), 31.30 (6 C, CH2),
31.96 (6 C, CH2), 36.47 (2 C, CH2), 41.59 (2 C, CH2), 59.53 (2 C,
quat. C-N), 59.79 (6 C, quat. C-N), 122.62, 124.84, 126.98, 129.85,
133.66, 136.58 (20 C, Ar-C), 166.29 (2 C, CONRCO), 177, 20 (6 C,
3
1.96 (m, 24 H, CH2), 2.19 (m, 26 H, CH2), 2.75 (t, J = 6.69 Hz, 2
H, CH2), 3.28 (br. s, 2 H, NH2), 6.40 (br. s, 3 H, NH), 7.30 (br. s,
1 H, NH) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ = 25.56,
26.24 (2 C, CH2), 28.05 (27 C, CH3), 29.70, 29.80 (18 C, CH2),
30.66 (1 C, CH2), 31.72, 31.92 (6 C, CH2), 36.67 (1 C, CH2), 40.94
(1 C, CH2-NH2), 57.52 (3 C, quat. C-N), 58.18 (1 C, quat. C-N),
80.55 (9 C, quat. C tBu), 172.80 (9 C, COOR), 173.19 (3 C,
NHCO), 173.60 (1 C, NHCO) ppm. IR: ν = 3277, 2980, 2934,
˜
1725, 1652, 1544, 1455, 1420, 1396, 1366, 1316, 1254, 1216, 1146,
1104, 1038, 953, 849, 757, 687 cm–1. C82H145N5O22 (1553)ϫ0.5
CHCl3: C 61.44, H 9.09, N 4.34; found C 61.63, H 8.86, N 4.54.
CONH), 179.72 (2 C, CONH), 181.02 (18 C, COOH) ppm. IR: ν
˜
= 2930, 2856, 2706–2559, 1691, 1644, 1594, 1544, 1444, 1405, 1343,
1293, 1185, 1139, 1104, 834, 799, 745, 722 cm–1. UV/Vis (phosphate
N,NЈ-Substituted Perylene-3,4:9,10-tetracarboxdiimide 3a: Prepared
from 9a (1.00 g, 1.89 mmol) and PTCDA (0.376 g, 0.95 mmol).
Purified by column chromatography in CHCl3. Yield 1.03 g
(78.5%). 1H NMR (300 MHz, CDCl3, 25 °C): δ = 1.41 (s, 54 H,
CH3), 1.48 (m, 4 H, CH2), 1.75 (m, 12 H, CH2), 1.96 (m, 12 H,
CH2), 2.20 (m, 16 H, CH2), 4.15 (t, 3J = 7.16 Hz, 4 H, CH2-N),
5.94 (br. s, 2 H, NH), 8.19 (m, 4 H, Ar-CH), 8.39 (m, 4 H, Ar-CH)
ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ = 25.32, 26.61, 27.47
(6 C, CH2), 28.01 (18 C, CH3), 29.73 (6 C, CH2), 29.81 (6 C, CH2),
37.13 (2 C, CH2), 40.28 (2 C, CH2), 57.21 (2 C, quat. C-N), 80.53
(6 C, quat. C tBu), 122.67, 122.91, 125.64, 128.77, 130.85, 133.83
(20 C, Ar-C), 162.88 (4 C, CON), 172.40 (2 C, CONH), 172.83 (6
buffer solution, pH 7.2): λmax = 497 nm, 533; fluorescence: λmax
=
547 nm, 588. C116H150N10O48 (2452)ϫ7 HCOOH: C 53.24, H 5.96,
N 5.05; found C 53.08, H 6.28, N 5.07.
N,NЈ-Substituted Perylene-3,4:9,10-tetracarboxdiimide 4a: Prepared
from 9a (0.110 g, 0.208 mmol) and N-dodecyl-3,4,9,10-perylenete-
tracarboxylic 3,4-anhydride 9,10-imide (0.122 g, 0.218 mmol). Puri-
fied by column chromatography with CHCl3. Yield 0.066 g
(56.18%). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 0.86 (t, 3J =
6.84 Hz, 3 H, CH3), 1.27 (br. m, 14 H, CH2), 1.39 (br. m, 2 H,
CH2), 1.42 (s, 27 H, CH3), 1.49 (m, 2 H, CH2), 1.76 (m, 8 H, CH2),
1.97 (m, 6 H, CH2), 2.20 (m, 8 H, CH2), 4.15 (m, 4 H, CH2), 5.92
(s, 1 H, NH), 8.20 (m, 4 H, Ar-H), 8.40 (m, 4 H, Ar-H) ppm. 13C
NMR (100 MHz, CDCl3, 25 °C): δ = 14.09 (1 C, CH3), 22.66,
25.32, 26.61, 27.17, 27.49 (5 C, CH2), 28.04 (3 C, CH3), 29.33,
29.78, 29.57 (3 C, CH2), 29.62 (3 C, CH2), 29.64 (broad, 2 C, CH2),
29.78 (3 C, CH2), 29.88 (broad, 2 C, CH2), 31.90 (1 C, CH2), 37.17
(1 C, CH2), 40.29, 40.70 (2 C, CH2), 57.26 (1 C, quat. C-N), 80.57
(3 C, quart- C tBu), 122.65, 122.94, 123.01, 125.69, 128.80, 128.81,
130.81, 130.87, 133.82, 133.87 (20 C, CH2), 162.90, 162.91 (4 C,
C, COOR) ppm. IR: ν = 3323, 2976, 2934, 2868, 1729, 1698, 1656,
˜
1594, 1540, 1455, 1405, 1366, 1316, 1251, 1216, 1150, 1104, 1038,
953, 849, 811, 745 cm–1. UV/Vis (CHCl3): λmax = 458 nm, 489, 526;
fluorescence: λmax = 533 nm, 575, 622. C80H108N4O18 (1413)ϫ0.25
CHCl3: C 66.77, H 7.56, N 3.88; found C 66.70, H 7.24, N 3.97.
N,NЈ-Substituted Perylene-3,4:9,10-tetracarboxdiimide 3b: Prepared
from 9b (0.403 g, 0.259 mmol) and PTCDA (0.051 g, 0.131 mmol).
Purified by column chromatography with ethyl acetate. Yield
0.293 g (65.25%). 1H NMR (400 MHz, CDCl3, 25 °C): δ = 1.35 (s,
162 H, CH3 + m. 4 H, CH2), 1.64 (m, 4 H, CH2), 1.74 (m, 4 H,
CH2), 1.95 (m, 48 H, CH2), 2.13 (m, 52 H, CH2), 4.16 (t, 3J =
6.47 Hz, 4 H, CH2-N), 6.15 (br. s, 6 H, NH), 7.22 (br. s, 2 H, NH),
8.58 (m, 8 H, Ar-CH) ppm. 13C NMR (100 MHz, CDCl3, 25 °C):
δ = 25.01, 26.45, 27.58 (6 C, CH2), 27.91 (54 C, CH3), 29.63 (18 C,
CH2), 29.66 (18 C, CH2), 31.54 (6 C, CH2), 31.63 (6 C, CH2), 36.73
CON), 172.39 (1 C, CONH), 172.85 (3 C, COOR) ppm. IR: ν =
˜
2922, 2853, 1725, 1695, 1652, 1594, 1540, 1440, 1405, 1343, 1247,
1150, 1100, 1038, 1015, 953, 849, 811, 745, 676 cm–1. UV/Vis
(CHCl3): λmax = 458 nm, 489, 526; fluorescence: λmax = 533 nm,
575, 622. C64H83N3O11 (1070)ϫ0.5 CHCl3: C 68.55, H 7.45, N
3.72; found C 68.44, H 7.47, N 3.85.
N,NЈ-Substituted Perylene-3,4:9,10-tetracarboxdiimide 4b: Prepared
(2 C, CH2CO), 40.35 (6 C, CH2), 57.30 (6 C, quat. C-N), 60.26 (2 from 9b (0.575 g, 0.037 mmol) and N-dodecyl-3,4,9,10-perylenete-
Eur. J. Org. Chem. 2007, 5497–5505
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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