Macromolecules
Scheme 1. Synthesis and Separation of Three Diamines 11TPE-NH , 12TPE-NH , and Z-12TPE-NH
Article
2
2
7
6
.14 (m, 6H), 7.12−7.04 (m, 8H), 6.98 (d, J = 8.5 Hz, 4H), 6.94−
dissolved with DMAc and dropped into ethanol to precipitate, which
was subsequently washed with hot ethanol and water, obtaining a
yellow powder.
.85 (m, 8H), 6.79 (d, J = 9.3 Hz, 4H), 3.83 (s, 6H, −OCH ).
3
−1
1
Z-12TPE-NO : FTIR (KBr): 1581, 1314 cm (−NO stretch). H
2
2
11-TPE-PA: FTIR (KBr): 3324, 1682 cm− (amide group). H
1
1
NMR (300 MHz, CDCl -d , δ/ppm): 7.97 (d, J = 9.3 Hz, 4H), 7.17−
3
6
7.11 (m, 6H), 7.10−7.04 (m, 8H), 7.01 (d, J = 8.6 Hz, 4H), 6.95−
6.84 (m, 8H), 6.80 (d, J = 9.3 Hz, 4H), 3.79 (s, 6H, −OCH ).
NMR (300 MHz, DMSO-d , δ/ppm): 9.77 (s, 2H, −NHCO), 7.46
6
(d, J = 8.9 Hz, 4H, H ), 7.21−6.99 (m, 8H, H + H ), 6.95−6.79 (m,
3
a
h
g
General Procedure for the Synthesis of TPE-NH (11TPE-
14H, H + H + H + H ), 6.76 (d, J = 6.9 Hz, 4H, H ), 6.52 (d, J = 7.8
2
i f e b c
NH , E-12TPE-NH , and Z-12TPE-NH ). TPE-NO (4.9 mmol, 4.0
Hz, 4H, H ), 3.68 (s, 6H, −OCH ), 2.34−2.23 (m, 2H, H ), 1.92−
2
2
2
2
d
3
j
g) was dissolved in a mixed solvent (15 mL of ethanol and 25 mL of
,4-dioxane) and 10% Pd/C (1.8 g) was added. The suspension
1.74 (m, 4H, H ), 1.52−1.33 (m, 4H, H ).
k
l
−
1
1
1
E-12TPE-PA: FTIR (KBr): 3324, 1682 cm (amide group). H
solution was heated and hydrazine monohydrate (6.1 g) was added
slowly within 30 min to keep the system at reflux. After being stirred
under reflux for 18 h, Pd/C was filtered from the hot reaction solution
and a yellow product was precipitated from the filtrate at room
temperature.
NMR (300 MHz, DMSO-d , δ/ppm): 9.81 (s, 2H, −NHCO), 7.49
6
(d, J = 7.7 Hz, 4H, H ), 7.22−7.07 (m, 6H, H + H ), 7.04−6.65 (m,
a
h
i
20H, H + H + H + H + H ), 6.57 (d, J = 23.7 Hz, 4H, H ), 3.71 (s,
b
e
f
c
g
d
6H, −OCH ), 2.39−2.25 (m, 2H, H ), 1.99−1.74 (m, 4H, H ), 1.59−
3
j
k
1.35 (m, 4H, H ).
Z-12TPE-PA: FTIR (KBr): 3324, 1682 cm (amide group). H
l
−1
−1
1
1
1TPE-NH (3.3 g, 89% yield): FTIR (KBr): 3463, 3383 cm
2
1
(
7
−NH stretch). H NMR (600 MHz, DMSO-d , δ/ppm): 7.13 (t, J =
NMR (300 MHz, DMSO-d , δ/ppm): 9.81 (s, 2H, −NHCO), 7.52
2
6
6
.3 Hz, 4H, H ), 7.08 (t, J = 7.3 Hz, 2H, H ), 6.96−6.90 (m, 8H, H +
(d, J = 9.0 Hz, 4H, H ), 7.14−7.04 (m, 6H, H + H ), 7.00−6.75 (m,
h
i
g
a
h
i
H ), 6.84 (d, J = 9.1 Hz, 4H, H ), 6.74 (d, J = 8.7 Hz, 4H, H ), 6.71
20H, H + H + H + H + H ), 6.61 (d, J = 8.6 Hz, 4H, H ), 3.70 (s,
f
e
c
b e f c g d
(
d, J = 8.8 Hz, 4H, H ), 6.53 (d, J = 8.7 Hz, 4H, H ), 6.43 (d, J = 8.8
6H, −OCH ), 2.37−2.24 (m, 2H, H ), 1.95−1.78 (m, 4H, H ), 1.52−
b
d
3
j
k
Hz, 4H, H ), 5.01 (s, 4H, −NH ), 3.70 (s, 6H, −OCH ).
1.38 (m, 4H, H ).
a
2
3
l
−
1
E-12TPE-NH (3.1 g, 85% yield): FTIR (KBr): 3463, 3383 cm
General Procedure for the Synthesis of Model Compounds
(11TPE-M, E-12TPE-M, and Z-12TPE-M). A mixture of TPE-2NH
2
2
1
(
7
−NH stretch). H NMR (600 MHz, DMSO-d , δ/ppm): 7.08 (t, J =
2
6
.2 Hz, 4H, H ), 7.04 (t, J = 7.2 Hz, 2H, H ), 6.99−6.94 (m, 8H, H +
(1 mmol, 0.7570 g), CHDA (2 mmol, 0.344 g), triphenyl phosphite
(1 mL), pyridine (0.5 mL), and NMP (2.5 mL) was heated at 120 °C
for 12 h. After cooling down to room temperature, the product was
precipitated from the solution to obtain a yellow powder.
h
i
g
H ), 6.85 (d, J = 9.1 Hz, 4H, H ), 6.79 (d, J = 8.7 Hz, 4H, H ), 6.70
f
e
c
(
d, J = 8.8 Hz, 4H, H ), 6.56 (d, J = 8.7 Hz, 4H, H ), 6.49 (d, J = 8.8
b
d
Hz, 4H, H ), 5.04 (s, 4H, −NH ), 3.72 (s, 6H, −OCH ).
a
2
3
−1
−1
1
Z-12TPE-NH (3.3 g, 89% yield): FTIR (KBr): 3463, 3383 cm
11TPE-M: FTIR (KBr): 3316, 1668 cm (amide group). H NMR
(300 MHz, DMSO-d , δ/ppm): 9.74 (s, 2H, −NHCO), 7.49 (d, J =
8.7 Hz, 4H, H ), 7.21−7.07 (m, 6H, H + H ), 6.99−6.83 (m, 16H,
+ H + H + H ), 6.80 (d, J = 8.4 Hz, 4H, H ), 6.56 (d, J = 8.3 Hz,
4H, H ), 3.72 (s, 6H, −OCH ), 2.35−2.23 (m, 2H, H
(m, 8H, H ), 1.69−1.16 (m, 12H, H + H ).
2
1
(
7
−NH stretch). H NMR (600 MHz, DMSO-d , δ/ppm): 7.16 (t, J =
6
2
6
.3 Hz, 4H, H ), 7.10 (t, J = 7.3 Hz, 2H, H ), 7.00 (d, J = 7.0 Hz, 4H,
a
h
i
h
i
H ), 6.91 (d, J = 9.0 Hz, 4H, H ), 6.83 (d, J = 9.1 Hz, 4H, H ), 6.74
H
g
f
e
b
c
g
f
e
(
d, J = 8.7 Hz, 4H, H ), 6.65 (d, J = 8.8 Hz, 4H, H ), 6.52 (d, J = 8.7
d
3
j
), 1.83−1.68
c
b
Hz, 4H, H ), 6.41 (d, J = 8.8 Hz, 4H, H ), 5.00 (s, 4H, −NH ), 3.70
k
l
m
d
a
2
−
1
1
(
s, 6H, −OCH ).
E-12TPE-M: FTIR (KBr): 3316, 1668 cm (amide group). H
3
General Procedure for the Synthesis of TPE-PA (11TPE-PA,
NMR (300 MHz, DMSO-d
6
, δ/ppm): 9.73 (s, 2H, −NHCO), 7.48
E-12TPE-PA, and Z-12TPE-PA). TPE-2NH (2 mmol, 1.5139 g),
(d, J = 8.9 Hz, 4H, H ), 7.22−7.11 (m, 6H, H + H ), 7.01 (d, J = 6.7
2
a
h
i
trans-1,4-CHDA (2 mmol, 0.3444 g), calcium chloride (0.3 g),
triphenyl phosphit (2.0 mL), pyridine (1.0 mL), and NMP (5.4 mL)
were mixed under a nitrogen atmosphere. At 120 °C, the dilute
solution gradually turned into a viscous solution, which was cooled to
room temperature after 5 h and poured into stirred ethanol,
producing a fiber-like solid. For the purification, the precipitate was
Hz, 4H, H ), 6.92 (d, J = 9.2 Hz, 4H, H ), 6.90−6.82 (m, 8H, H +
g
f
b
H ), 6.74 (d, J = 8.5 Hz, 4H, H ), 6.54 (d, J = 8.7 Hz, 4H, H ), 3.72
e
c
d
(s, 6H, −OCH ), 2.34−2.23 (m, 2H, H ), 1.82−1.69 (m, 8H, H ),
3
j
k
1.67−1.16 (m, 12H, H + H ).
l
m
−
1
1
Z-12TPE-M: FTIR (KBr): 3316, 1668 cm (amide group). H
NMR (300 MHz, DMSO-d , δ/ppm): 9.75 (s, 2H, −NHCO), 7.52
6
C
Macromolecules XXXX, XXX, XXX−XXX