W. Zhu, et al.
Dyes and Pigments 171 (2019) 107740
N ,N -bis((S)-1-oxo-1-((4-(10,15,20-triphenylporphyrin-5-yl)
phenyl)amino)propan-2-yl)pyridine-2,6-dicarboxamide (D-4). The
general synthetic procedure is the same as that of L-4, with the ex-
ception that D-1 was used instead. The target compound D-4 was ob-
2
6
AVANCE II 400 spectrometer using CDCl
3
(δ = 7.26 ppm) as an internal
reference. Cyclic voltammetry (CV) and differential pulse voltammetry
DPV) measurements were carried out using a Chi-730D electro-
chemistry station with a three-electrode cell that includes glassy carbon
working electrode, Φ = 3 mm), Pt wire (counter electrode,
(
(
tained in 83.09% yield (59 mg). High-resolution ESI-MS: m/
z = 1533.6058 (Calcd: [M]+ = 1533.6015).
1
H NMR (400 MHz,
Φ = 0.2 mm) and Ag/AgCl (reference) electrodes. All electrochemical
characterizations were performed in ortho-dichlorobenzene (o-DCB), a
solvent with low polarity, under an N atmosphere containing 0.1 M
2
Chloroform-d) δ 9.36 (s, 2H), 9.17 (d, J = 7.8 Hz, 2H), 8.93–8.79 (m,
16H), 8.42 (d, J = 7.8 Hz, 2H), 8.27–8.05 (m, 21H), 7.96 (t, J = 7.8 Hz,
1H), 7.82–7.72 (m, 6H), 7.66 (ddt, J = 11.9, 7.7, 4.0 Hz, 13H), 1.91 (d,
tetrabutylammonium perchlorate (TBAP) as the supporting electrolyte.
UV–visible absorption spectra were recorded on a Shimadzu UV3600
spectrophotometer. Fourier transform infrared spectra (FT-IR) were
recorded on a Nicolet Nexus 470 FT-IR spectrophotometer by using the
KBr disk method. CD spectra were recorded on a JASCO J-815 spec-
tropolarimeter. Fluorescence spectra were recorded on CARY Eclipse
fluorescence spectrophotometer from Varian Australia (Model NO.
EL01064834).
−1
J = 7.0 Hz, 6H), −2.75 (s, 4H). IR (KBr): ν, cm 3314 (m), 3056 (w),
3025 (w), 2704 (w), 2602 (w), 2532 (w), 1674 (s), 1596 (s), 1511 (vs),
1472 (m), 1441 (w), 1400 (w), 1350 (m), 1244 (w), 1182 (w), 1000
(w), 980 (w), 965 (vs), 800 (vs), 730 (m), 700 (s).
2
5
N ,N -bis((R)-1-oxo-1-((4-(10,15,20-triphenylporphyrin-5-yl)
phenyl)amino)propan-2-yl)furan-2,5-dicarboxamide (L-5). The
general synthetic procedure is same that of L-3, except furan-2,5-di-
carboxylate acid was used instead. The target compound L-5 was ob-
2
.2. Synthesis
tained in a 70.3% yield (45 mg). High-resolution ESI-MS: m/
z = 1522.5963 (Calcd: [M+H] = 1523.5955). 1H NMR (400 MHz,
Chloroform-d) δ 9.15 (s, 2H), 8.86 (d, J = 4.8 Hz, 4H), 8.81 (q,
J = 4.7 Hz, 13H), 8.23–8.16 (m, 8H), 8.12 (d, J = 7.2 Hz, 9H), 8.04 (d,
J = 8.2 Hz, 6H), 7.81–7.69 (m, 6H), 7.62 (s, 13H), 1.79 (d, J = 6.7 Hz,
+
2
5
N ,N -bis((R)-1-oxo-1-((4-(10,15,20-triphenylporphyrin-5-yl)
phenyl)amino)propan-2-yl)pyridine-2,5-dicarboxamide (L-3).
Pyridine-2,5-dicarboxylic acid (100 mg, 0.59 mmol) was mixed with
−
1
2
mL of SOCl
2
. The reaction mixture was refluxed at 85 °C for 3 h under
6H), −2.79 (s, 4H). IR (KBr): ν, cm
3319 (m), 3057 (w), 3030 (w),
N
2
to afford pyridine-2,5-dicarbonyl dichloride (PDC). Excess SOCl
2
2703 (w), 2606 (w), 2537 (w), 1661 (s), 1595 (s), 1513 (vs), 1472 (m),
1439 (w), 1400 (w), 1349 (m), 1250 (w), 1182 (w), 1002 (w), 981 (w),
965 (vs), 800 (vs), 728 (m), 700 (s).
N ,N -bis((S)-1-oxo-1-((4-(10,15,20-triphenylporphyrin-5-yl)
phenyl)amino)propan-2-yl)furan-2,5-dicarboxamide (D-5). The
general synthetic procedure is the same as that of L-5, with the ex-
ception that D-1 was used instead. The target compound D-5 was ob-
was removed by distillation under high vacuum. 9.54 mg
(
0.0456 mmol) of pyridine-2,5-dicarbonyl dichloride (PDC) and L-1
80 mg, 0.114 mmol) were dissolved in 15 mL of CH Cl , followed by
N. The reaction mixture was stirred at room
temperature for 3 h to afford L-3. The obtained product was dried on a
rotary evaporator, purified with a silica column (eluent: CH OH/
CH Cl , 3:97, v/v), followed by purification using GPC (eluent: CHCl
and dried in vacuo affording a purple colour solid L-3 in 70.4% yield
2
5
(
2
2
addition of 1 drop of Et
3
3
2
2
3
)
tained in a 71.8% yield (46 mg). High-resolution ESI-MS: m/
z = 1522.5968 (Calcd: [M+H] = 1523.5955). 1H NMR (400 MHz,
Chloroform-d) δ 9.15 (s, 2H), 8.86 (d, J = 4.8 Hz, 4H), 8.81 (q,
J = 4.8 Hz, 12H), 8.23–8.16 (m, 9H), 8.12 (d, J = 7.4 Hz, 10H), 8.04
(d, J = 7.9 Hz, 6H), 7.78–7.72 (m, 6H), 7.62 (s, 13H), 1.79 (d,
+
(
50 mg). High-resolution ESI-MS: m/z = 1533.6122 (Calcd: [M
+
1
+
H] = 1533.6115). H NMR (400 MHz, Chloroform-d) δ 9.17 (s, 1H),
9.05 (s, 1H), 8.88–8.76 (m, 17H), 8.66–8.55 (m, 3H), 8.43 (s, 2H), 8.18
−1
(
dd, J = 20.1, 6.9 Hz, 17H), 7.97 (d, J = 7.6 Hz, 4H), 7.77–7.65 (m,
J = 6.3 Hz, 6H), −2.78 (s, 4H). IR (KBr): ν, cm 3315 (m), 3054 (w),
3025 (w), 2702 (w), 2604 (w), 2533 (w), 1667 (s), 1594 (s), 1513 (vs),
1473 (m), 1439 (w), 1400 (w), 1351 (m), 1247 (w), 1181 (w), 1002
(w), 982 (w), 965 (vs), 800 (vs), 729 (m), 701 (s).
−
1
1
3
1
1
8H), 1.79 (dd, J = 9.3, 7.0 Hz, 6H), −2.80 (s, 4H). IR (KBr): ν, cm
315 (m), 3054 (w), 3026 (w), 2702 (w), 2600 (w), 2529 (w), 1666 (s),
593 (s), 1508 (vs), 1469 (m), 1438 (w), 1400 (w), 1349 (m), 1245 (w),
180 (w), 1000 (w), 981 (w), 965 (vs), 800 (vs), 730 (m), 700 (s).
2
5
N ,N -bis((R)-1-oxo-3-phenyl-1-((4-(10,15,20-triphenylpor-
phyrin-5-yl)phenyl)amino) propan-2-yl)furan-2,5-dicarboxamide
(L-6). The general synthetic procedure is the same as that of L-3, with
the exception that L-2 was used instead. The target compound was
obtained in 61.4% yield (43 mg). High-resolution ESI-MS: m/
z = 1574.6598 (Calcd: [M+H] = 1523.6581). 1H NMR (400 MHz,
Chloroform-d) δ 8.87–8.79 (m, 18H), 8.56 (s, 1H), 8.23–8.14 (m, 19H),
7.84–7.66 (m, 26H), 7.46 (d, J = 11.5 Hz, 8H), 3.48 (d, J = 11.3 Hz,
2
5
N ,N -bis((S)-1-oxo-1-((4-(10,15,20-triphenylporphyrin-5-yl)
phenyl)amino)propan-2-yl)pyridine-2,5-dicarboxamide (D-3). The
general synthetic procedure is the same as that of L-3, with the ex-
ception that D-1 was used instead. The target compound D-3 was ob-
tained in 67.60% yield (48 mg). High-resolution ESI-MS: m/
+
+
z = 1533.6181 (Calcd: [M+H] = 1533.6115). 1H NMR (400 MHz,
Chloroform-d) δ 9.20 (d, J = 8.2 Hz, 2H), 8.92 (s, 1H), 8.84–8.70 (m,
−
1
1
7
7H), 8.49–8.40 (m, 2H), 8.22–7.95 (m, 21H), 7.79–7.70 (m, 6H),
.69–7.50 (m, 14H), 1.79 (dd, J = 14.9, 6.9 Hz, 6H), −2.81 (s, 4H). IR
4H), −2.79 (s, 4H). IR (KBr): ν, cm
3315 (m), 3058 (w), 3028 (w),
2700 (w), 2606 (w), 2534 (w), 1668 (s), 1594 (s), 1511 (vs), 1473 (m),
1439 (w), 1401 (w), 1349 (m), 1243 (w), 1180 (w), 1001 (w), 981 (w),
965 (vs), 800 (vs), 729 (m), 700 (s).
−
1
(
KBr): ν, cm
3315 (m), 3052 (w), 3025 (w), 2705 (w), 2605 (w),
2
1
7
534 (w), 1667 (s), 1595 (s), 1509 (vs), 1470 (m), 1440 (w), 1400 (w),
350 (m), 1246 (w), 1180 (w), 1000 (w), 981 (w), 965 (vs), 800 (vs),
28 (m), 700 (s).
2
5
N ,N -bis((S)-1-oxo-3-phenyl-1-((4-(10,15,20-triphenylpor-
phyrin-5-yl)phenyl)amino) propan-2-yl)furan-2,5-dicarboxamide
(D-6). The general synthetic procedure is the same as that of L-6, with
the exception that D-2 was used instead. The target compound was
obtained in 58.5% yield (41 mg). High-resolution ESI-MS: m/
z = 1574.6588 (Calcd: [M+H] = 1523.6581). 1H NMR (400 MHz,
Chloroform-d) δ 8.92–8.73 (m, 18H), 8.56 (s, 1H), 8.38 (s, 2H),
8.23–8.12 (m, 17H), 7.87–7.63 (m, 25H), 7.46 (s, 9H), 3.47 (s, 4H),
2
6
N ,N -bis((R)-1-oxo-1-((4-(10,15,20-triphenylporphyrin-5-yl)
phenyl)amino)propan-2-yl)pyridine-2,6-dicarboxamide (L-4). The
general synthetic procedure is the same as that of L-3, with the ex-
ception that pyridine-2,6-dicarboxylate acid was used instead. The
+
target compound L-4 was obtained in 80.3% yield (57 mg). High-re-
solution ESI-MS: m/z = 1533.6088 (Calcd: [M] = 1533.6015). 1
+
H
−
1
NMR (400 MHz, Chloroform-d) δ 9.02 (s, 2H), 8.88–8.75 (m, 19H), 8.49
−2.79 (s, 4H). IR (KBr): ν, cm 3318 (m), 3058 (w), 3026 (w), 2700
(w), 2604 (w), 2531 (w), 1653 (s), 1595 (s), 1507 (vs), 1472 (m), 1439
(w), 1400 (w), 1351 (m), 1247 (w), 1181 (w), 1000 (w), 981 (w), 966
(vs), 800 (vs), 728 (m), 700 (s).
(
d, J = 7.8 Hz, 2H), 8.24–8.15 (m, 17H), 8.10 (t, J = 7.8 Hz, 1H), 8.02
(
d, J = 8.2 Hz, 4H), 7.79–7.69 (m, 18H), 1.88 (d, J = 7.0 Hz, 6H),
−
1
−
2.78 (s, 4H). IR (KBr): ν, cm 3315 (m), 3052 (w), 3024 (w), 2702
(
(
(
w), 2599 (w), 2531 (w), 1668 (s), 1595 (s), 1508 (vs), 1471 (m), 1439
w), 1400 (w), 1347 (m), 1244 (w), 1180 (w), 1000 (w), 981 (w), 966
vs), 800 (vs), 728 (m), 700 (s).
2