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sired TPP-H4,5,6 as a purple powder (274 mg, 86% yield). 1H NMR
(400 MHz, CDCl3): d=8.85 (s, 8H), 8.31 (s, 8H), 8.06 (s, 4H), 3.20 (s,
8H), À2.92 ppm (s, 2H); HRMS: m/z calcd for C60H31N4: 807.25487
[M+H]+; found: 807.25410.
(486.6), 347 (484.9), 425 (707.1), 519 (34.5), 555 (27.4), 593 (15.8),
649 nm (15.4103 mÀ1 cmÀ1); HRMS: m/z calcd for C260H239N4:
3416.8819 [M+H]+; found: 3416.8821; elemental analysis calcd (%)
for C260H238N4: C 91.34, H 7.02, N 1.64; found: C 91.05, H 6.93, N
1.77.
TPP1: A mixture of 3 (400 mg, 1.36 mmol, 1 equiv) and propionic
acid (5 mL) was heated at 1208C. After reaching that temperature,
pyrrole (0.095 mL, 1.36 mmol, 1 equiv) in propionic acid (1 mL) was
added dropwise into the mixture and the reaction was heated at
reflux for 1.5 h. After cooling down at room temperature, MeOH
was added and the reaction medium was filtered. The solid residue
was then purified by chromatography using a petroleum ether/
CH2Cl2 (5:1) mixture as eluent. The title compound was isolated as
a purple powder (80 mg, 17% yield). 1H NMR (400 MHz, CDCl3,
ppm): d=8.92 (s, 8H), 8.24 (d, J=7.2 Hz, 8H), 7.97 (d, J=7.2 Hz,
8H), 7.88-7.85 (m, 12H), 7.73 (d, J=8 Hz, 4H), 7.60 (d, J=6.4 Hz,
4H), 7.43 (t, J=6.8 Hz, 4H), 7.36 (t, J=6.8 Hz, 4H), 4.00 (s, 8H),
À2.74 ppm (s, 2H); UV/Vis (CH2Cl2): lmax =320, 426, 518, 554, 592,
650 nm; HRMS: m/z calcd for C104H63N4: 1366.4974 [M+H]+; found:
1367.5200; elemental analysis calcd (%) for C104H62N4: C 91.33, H
4.57, N 4.10; found: C 91.06, H 4.39,N 4.08.
TPP4: A mixture of 5 (850 mg, 1.76 mmol, 1 equiv) and propionic
acid (40 mL) was heated at 1208C. After reaching that temperature,
pyrrole (0.12 mL, 1.76 mmol, 1 equiv) in propionic acid (1 mL) was
added dropwise into the mixture and the reaction was heated at
reflux for 3 h. After cooling down at room temperature, MeOH was
added and the reaction medium was filtered and washed further
with MeOH. The solid residue was recrystallized by CH2Cl2. The title
compound was isolated as a light-brown powder (20 mg, 2%
1
yield). H NMR (400 MHz, CDCl3,): 9.03 (s, 8H), 8.42 (s, 8H), 8.20 (s,
4H), 7.78-7.76 (m, 24H), 7.62 (d, J=8.8 Hz, 8H), 7.53 (d, J=7.6 Hz,
8H), 7.38 (t, J=7.6 Hz, 8H), 7.31 (t, J=7.2 Hz, 8H), 3.91 (s, 16H),
À2.75 ppm (s, 2H); UV/Vis (CH2Cl2): lmax =324, 428, 517, 552, 589,
646 nm; HRMS: m/z calcd for C164H95N4: 2118.7478 [M+H]+; found:
2119.7510; elemental analysis calcd (%) for C164H94N4: C 92.89, H
4.47, N 2.64; found: C 92.48, H 4.44, N 2.59.
TPP2: A mixture of aldehyde 4 (700 mg, 1.72 mmol, 1 equiv) and
propionic acid (6.5 mL) was heated to 1208C. After dropwise addi-
tion of a solution of pyrrole (0.12 mL, 1.72 mmol, 1 equiv) in pro-
pionic acid (1.0 mL), the reaction medium was heated at reflux for
a further 1.5 h. After cooling at room temperature, MeOH was
added to the reaction mixture and the precipitate was filtered. The
residue could be purified by repeated chromatography on silica
using petroleum ether/CH2Cl2 (1:1) as eluent. The title compound
TPP5: A mixture of aldehyde 6 (860 mg, 1.22 mmol, 1 equiv) and
propionic acid (6 mL) was heated to 1208C. After dropwise addi-
tion of a solution of pyrrole (0.085 mL, 1.22 mmol, 1 equiv) in pro-
pionic acid (1.0 mL), the reaction medium was heated at reflux for
a further 3.0 h. After cooling to room temperature, MeOH was
added to the reaction mixture and the precipitate was filtered. The
residue could be purified by repeated chromatography on silica
using petroleum ether/CH2Cl2 (5:1) as eluent. The title compound
was isolated as red powder, and subsequently recrystallized from
hot CHCl3 solutions upon addition of excess MeOH (165 mg, 18%
1
was isolated as a rose-purple powder (220 mg, 28% yield). H NMR
3
(400 MHz, CDCl3,): d=8.92 (s, 8H), 8.24 (d, JHH =7.6 Hz, 8H), 7.99
(d, 3JHH =7.6 Hz, 8H), 7.78–7.75 (m, 8H), 7.69–7.67 (m, 8H), 7.40–
yield). H NMR (400 MHz, CDCl3,): d=9.02 (s, 8H), 8.43 (s, 8H), 8.26
1
3
3
7.35 (m, 12H), 2.05 (t, JHH =8.0 Hz, 16H), 1.19–1.10 (m, 16H), 0.73
(s, 4H), 7.67 (d, JHH =7.2 Hz, 16H), 7.59-7.57 (m, 16H), 7.31 (broad,
(t, 3JHH =7.2 Hz, 24H), 0.69–0.60 (m, 16H), À2.74 ppm (s, 2H);
13C{1H} NMR (100 MHz, CDCl3,): d=151.1 (s), 150.9 (s), 141.9 (s),
141.7 (s), 140.4 (s), 134.6 (s), 130.8 (s), 130.0 (s), 127.6 (s), 126.9 (s),
126.1 (s), 123.1 (s), 122.9 (s), 121.4 (s), 120.1 (s), 119.7 (s), 91.9 (s),
89.3 (s), 55.1 (s), 40.2 (s), 26.0 (s), 23.1 (s), 13.9 ppm (s); UV/Vis
(CH2Cl2): lmax (e)=323 (178.4), 427 (670.2), 519 (36.0), 556 (30.1),
592 (17.2), 649 nm (17.1103 mÀ1 cmÀ1); HRMS: m/z calcd for
C136H127N4: 1815.9982 [M+H]+; found: 1816.0055; elemental analy-
sis calcd (%) for C136H126N4: C 89.92, H 6.99, N 3.08; found: C 89.65,
H 6.59, N 3.12.
24H), 1.95 (t, JHH =8.0 Hz, 32H), 1.07-1.02 (m, 32H), 0.65-0.48 (m,
3
80H), À2.75 ppm (s, 2H); 13C{1H} NMR (100 MHz, CDCl3,): d=151.1
(s), 150.8 (s), 142.5 (s), 141.8 (s), 140.3 (s), 136.7 (s), 134.0 (s), 130.8
(s), 127.6 (s), 126.9 (s), 126.2 (s), 122.9 (s), 122.6 (s), 121.0 (s), 120.0
(s), 119.7 (s), 118.7 (s), 91.6 (s), 88.6 (s), 55.1 (s), 40.1 (s), 25.9 (s),
23.0 (s), 13.8 ppm (s); UV/Vis (CH2Cl2): lmax (e)=327 (393.5), 427
(806.6), 517 (50.8), 551 (30.9), 590 (27.8), 646 nm (22.4
103 mÀ1 cmÀ1); HRMS: m/z calcd for C228H223N4: 3016.7567 [M+H]+;
found: 3016.7647; elemental analysis calcd (%) for C228H222N4: C
90.73, H 7.41, N 1.86; found: C 90.39, H 7.38, N 1.93.
TPP3: A mixture of aldehyde 8 (312 mg, 0.39 mmol, 1 equiv) and
propionic acid (2 mL) was heated to 1208C. After dropwise addi-
tion of a solution of pyrrole (0.03 mL, 0.39 mmol, 1 equiv) in pro-
pionic acid (0.5 mL), the reaction medium was heated at reflux for
a further for 5.5 h. After cooling to room temperature, MeOH was
added to the reaction mixture and the precipitate was filtered. The
residue could be purified by repeated chromatography on silica
using petroleum ether/CH2Cl2 (5:1) as eluent. The title compound
was initially isolated as red powder, and subsequently recrystallized
from hot CHCl3 solutions upon addition of excess MeOH, giving
eventually the title compound as a dark-purple powder (72 mg,
22% yield). 1H NMR (400 MHz, CDCl3, ppm): d=8.94 (s, 8H), 8.28
TPP6: A mixture of aldehyde 9 (500 mg, 0.33 mmol, 1 equiv) and
propionic acid (3 mL) was heated to 1208C. After dropwise addi-
tion of a solution of pyrrole (0.085 mL, 1.22 mmol, 1 equiv) in pro-
pionic acid (0.5 mL), the reaction medium was heated at reflux for
a further 5.5 h. After cooling to room temperature, MeOH was
added to the reaction mixture and the precipitate was filtered. The
residue could be purified by repeated chromatography on silica
using petroleum ether/CH2Cl2 (5:1) as eluent. The title compound
was initially isolated as red powder, and subsequently recrystallized
from hot CHCl3 solutions upon addition of excess MeOH, giving
eventually the desired compound 1d as a dark-purple powder
1
(66 mg, 13% yield). H NMR (400 MHz, CDCl3,): d=9.08 (s, 8H), 8.46
3
3
(d, JHH =8.0 Hz, 8H), 7.99 (d, JHH =8.0 Hz, 8H), 7.87 (s, 8H), 7.83 (s,
(s, 8H), 8.22 (s, 4H), 7.77–7.74 (m, 20H), 7.65-7.61 (m, 32H), 7.52–
3
3
4H), 7.73 (d, JHH =8.0 Hz, 16H), 7.59–7.57 (m, 16H), 7.39–7.32 (m,
7.47 (m, 36H), 7.36–7.28 (m, 48H), 1.91 (t, JHH =8.0 Hz, 64H), 1.05–
3
3
24H), 2.02 (t, JHH =8.0 Hz, 32H), 1.17–1.08 (m, 32H), 0.71 (t, JHH
=
0.99 (m, 64H), 0.63–0.52 (m, 160H), À2.70 ppm (s, 2H);
13C{1H} NMR (100 MHz, CDCl3,): d=151.0 (s), 150.8 (s), 141.8 (s),
140.3 (s), 134.4 (s), 134.0 (s), 130.7 (s), 127.6 (s), 126.8 (s), 126.1 (s),
124.4 (s), 124.0 (s), 123.6 (s), 122.9 (s), 122.2 (s), 120.8 (s), 120.0 (s),
119.6 (s), 91.9 (s), 89.4 (s), 89.1 (s), 87.8 (s), 55.0 (s), 40.1 (s), 25.8 (s),
23.0 (s), 13.8 ppm (s); UV/Vis (CH2Cl2): lmax (e)=327 (916.6), 348
(821.6), 426 (566.1), 517 (27.8), 551 (14.9), 590 (12.9), 645 nm (9.3
7.2 Hz, 48H), 0.67–0.58 (m, 32H), À2.72 ppm (s, 2H); 13C{1H} NMR
(100 MHz, CDCl3,): d=151.1 (s), 150.8 (s), 142.4 (s), 141.8 (s), 140.3
(s), 134.7 (s), 134.2 (s), 134.0 (s), 130.7 (s), 130.2 (s), 127.6 (s), 126.9
(s), 126.1 (s), 124.4 (s), 124.1 (s), 124.0 (s), 122.9 (s), 122.6 (s), 120.9
(s), 120.1 (s), 119.7 (s), 91.9 (s), 90.4 (s), 89.3 (s), 87.9 (s), 55.1 (s),
40.2 (s), 25.9 (s), 23.1 (s), 13.8 ppm (s); UV/Vis (CH2Cl2): lmax (e)=329
Chem. Eur. J. 2016, 22, 5583 – 5597
5595
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